Electrolyte-Gated Carbon Nanotube Field-Effect Transistor-Based Sensors for Nanoplastics Detection in Seawater: A Study of the Interaction between Nanoplastics and Carbon Nanotubes.

Plastics accumulating in the environment are nowadays of great concern for aquatic systems and for the living organisms populating them. In this context, nanoplastics (NPs) are considered the major and most dangerous contaminants because of their small size and active surface, which allow them to interact with a variety of other molecules. Current methods used for the detection of NPs rely on bulky and expensive techniques such as spectroscopy. Here we propose, for the first time, a novel, fast, and easy-to-use sensor based on an electrolyte-gated field-effect transistor (EG-FET) with a carbon nanotube (CNT) semiconductor (EG-CNTFET) for the detection of NPs in aquatic environments, using polystyrene NPs (PS-NPs) as a model material. In particular, as a working mechanism for the EG-CNTFETs we exploited the ability of CNTs and PS to form noncovalent interactions. Indeed, in our EG-CNTFET devices, the interaction between NPs and CNTs caused a change in the electric double layers. A linear increase in the corrected on current (*ION) of the EG-CNTFETs, with a sensitivity of 9.68 µA/(1 mg/mL) and a linear range of detection from 0.025 to 0.25 mg/mL were observed. A π-π interaction was hypothesized to take place between the two materials, as indicated by an X-ray photoelectron spectroscopy analysis. Using artificial seawater as an electrolyte, to mimic a real-case scenario, a linear increase in *ION was also observed, with a sensitivity of 6.19 µA/(1 mg/mL), proving the possibility to use the developed sensor in more complex solutions, as well as in low concentrations. This study offers a starting point for future exploitation of electrochemical sensors for NP detection and identification.

In vitro gastrointestinal gas monitoring with carbon nanotube sensors.

In vitro simulators of the human gastrointestinal (GI) tract are remarkable technological platforms for studying the impact of food on the gut microbiota, enabling continuous and real-time monitoring of key biomarkers. However, comprehensive real-time monitoring of gaseous biomarkers in these systems is required with a cost-effective approach, which has been challenging to perform experimentally to date. In this work, we demonstrate the integration and in-line use of carbon nanotube (CNT)-based chemiresitive gas sensors coated with a thin polydimethylsiloxane (PDMS) membrane for the continuous monitoring of gases within the Simulator of the Human Microbial Ecosystem (SHIME). The findings demonstrate the ability of the gas sensor to continuously monitor the different phases of gas production in this harsh, anaerobic, highly humid, and acidic environment for a long exposure time (16 h) without saturation. This establishes our sensor platform as an effective tool for real-time monitoring of gaseous biomarkers in in vitro systems like SHIME.

Polymeric integration of structure-switching aptamers on transistors for histamine sensing.

Aptamers that undergo large conformational rearrangements at the surface of electrolyte-gated field-effect transistor (EG-FETs)-based biosensors can overcome the Debye length limitation in physiological high ionic strength environments. For the sensitive detection of small molecules, carbon nanotubes (CNTs) that approach the dimensions of analytes of interest are promising channel materials for EG-FETs. However, functionalization of CNTs with bioreceptors using frequently reported surface modification strategies (e.g., π-π stacking), requires highly pristine CNTs deposited through methods that are incompatible with low-cost fabrication methods and flexible substrates. In this work, we explore alternative non-covalent surface chemistry to functionalize CNTs with aptamers. We harnessed the adhesive properties of poly-D-lysine (PDL), to coat the surface of CNTs and then grafted histamine-specific DNA aptamers electrostatically in close proximity to the CNT semiconducting channel. The layer-by-layer assembly was monitored by complementary techniques such as X-ray photoelectron spectroscopy, optical waveguide lightmode spectroscopy, and fluorescence microscopy. Surface characterization confirmed histamine aptamer integration into PDL-coated CNTs and revealed ∼5-fold higher aptamer surface coverage when using CNT networks with high surface areas. Specific aptamers assembled on EG-CNTFETs enabled histamine detection in undiluted high ionic strength solutions in the concentration range of 10 nM to 100 µM. Sequence specificity was demonstrated via parallel measurements with control EG-CNTFETs functionalized with scrambled DNA. Histamine aptamer-modified EG-CNTFETs showed high selectivity vs. histidine, the closest structural analog and precursor to histamine. Taken together, these results implied that target-specific aptamer conformational changes on CNTs facilitate signal transduction, which was corroborated by circular dichroism spectroscopy. Our work suggests that layer-by-layer polymer chemistry enables integration of structure-switching aptamers into flexible EG-CNTFETs for small-molecule biosensing.

Near Infrared Efficiency Enhancement of Silicon Photodiodes by Integration of Metal Nanostructures Supporting Surface Plasmon Polaritrons.

Recent years have witnessed a growing interest in detectors capable of detecting single photons in the near-infrared (NIR), mainly due to the emergence of new applications such as light detection and ranging (LiDAR) for, e.g., autonomous driving. A silicon single-photon avalanche diode is surely one of the most interesting and available technologies, although it yields a low efficiency due to the low absorption coefficient of Si in the NIR. Here, we aim at overcoming this limitation through the integration of complementary metal-oxide-semiconductor (CMOS) -compatible nanostructures on silicon photodetectors. Specifically, we utilize silver grating arrays supporting surface plasmons polaritons (SPPs) to superficially confine the incoming NIR photons and therefore to increase the probability of photons generating an electron-hole pair. First, the plasmonic silver array is geometrically designed using time domain simulation software to achieve maximum detector performance at 950 nm. Then, a plasmonic silver array characterized by a pitch of 535 nm, a dot width of 428 nm, and a metal thickness of 110 nm is integrated by means of the focused ion beam technique on the detector. Finally, the integrated detector is electro-optically characterized, demonstrating a QE of 13% at 950 nm, 2.2 times higher than the reference. This result suggests the realization of a silicon device capable of detecting single NIR photons, at a low cost and with compatibility with standard CMOS technology platforms.

Smart Approach for the Design of Highly Selective Aptamer-Based Biosensors.

Aptamers are chemically synthesized single-stranded DNA or RNA oligonucleotides widely used nowadays in sensors and nanoscale devices as highly sensitive biorecognition elements. With proper design, aptamers are able to bind to a specific target molecule with high selectivity. To date, the systematic evolution of ligands by exponential enrichment (SELEX) process is employed to isolate aptamers. Nevertheless, this method requires complex and time-consuming procedures. In silico methods comprising machine learning models have been recently proposed to reduce the time and cost of aptamer design. In this work, we present a new in silico approach allowing the generation of highly sensitive and selective RNA aptamers towards a specific target, here represented by ammonium dissolved in water. By using machine learning and bioinformatics tools, a rational design of aptamers is demonstrated. This "smart" SELEX method is experimentally proved by choosing the best five aptamer candidates obtained from the design process and applying them as functional elements in an electrochemical sensor to detect, as the target molecule, ammonium at different concentrations. We observed that the use of five different aptamers leads to a significant difference in the sensor's response. This can be explained by considering the aptamers' conformational change due to their interaction with the target molecule. We studied these conformational changes using a molecular dynamics simulation and suggested a possible explanation of the experimental observations. Finally, electrochemical measurements exposing the same sensors to different molecules were used to confirm the high selectivity of the designed aptamers. The proposed in silico SELEX approach can potentially reduce the cost and the time needed to identify the aptamers and potentially be applied to any target molecule.

Field-Effect Transistor-Based Biosensors for Environmental and Agricultural Monitoring.

The precise monitoring of environmental contaminants and agricultural plant stress factors, respectively responsible for damages to our ecosystems and crop losses, has nowadays become a topic of uttermost importance. This is also highlighted by the recent introduction of the so-called "Sustainable Development Goals" of the United Nations, which aim at reducing pollutants while implementing more sustainable food production practices, leading to a reduced impact on all ecosystems. In this context, the standard methods currently used in these fields represent a sub-optimal solution, being expensive, laboratory-based techniques, and typically requiring trained personnel with high expertise. Recent advances in both biotechnology and material science have led to the emergence of new sensing (and biosensing) technologies, enabling low-cost, precise, and real-time detection. An especially interesting category of biosensors is represented by field-effect transistor-based biosensors (bio-FETs), which enable the possibility of performing in situ, continuous, selective, and sensitive measurements of a wide palette of different parameters of interest. Furthermore, bio-FETs offer the possibility of being fabricated using innovative and sustainable materials, employing various device configurations, each customized for a specific application. In the specific field of environmental and agricultural monitoring, the exploitation of these devices is particularly attractive as it paves the way to early detection and intervention strategies useful to limit, or even completely avoid negative outcomes (such as diseases to animals or ecosystems losses). This review focuses exactly on bio-FETs for environmental and agricultural monitoring, highlighting the recent and most relevant studies. First, bio-FET technology is introduced, followed by a detailed description of the the most commonly employed configurations, the available device fabrication techniques, as well as the specific materials and recognition elements. Then, examples of studies employing bio-FETs for environmental and agricultural monitoring are presented, highlighting in detail advantages and disadvantages of available examples. Finally, in the discussion, the major challenges to be overcome (e.g., short device lifetime, small sensitivity and selectivity in complex media) are critically presented. Despite the current limitations and challenges, this review clearly shows that bio-FETs are extremely promising for new and disruptive innovations in these areas and others.

An Aptasensor Based on a Flexible Screen-Printed Silver Electrode for the Rapid Detection of Chlorpyrifos.

In this work, we propose a novel disposable flexible and screen-printed electrochemical aptamer-based sensor (aptasensor) for the rapid detection of chlorpyrifos (CPF). To optimize the process, various characterization procedures were employed, including Fourier transform infrared spectroscopy (FT-IR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). Initially, the aptasensor was optimized in terms of electrolyte pH, aptamer concentration, and incubation time for chlorpyrifos. Under optimal conditions, the aptasensor showed a wide linear range from 1 to 105 ng/mL with a calculated limit of detection as low as 0.097 ng/mL and sensitivity of 600.9 µA/ng. Additionally, the selectivity of the aptasensor was assessed by identifying any interference from other pesticides, which were found to be negligible (with a maximum standard deviation of 0.31 mA). Further, the stability of the sample was assessed over time, where the reported device showed high stability over a period of two weeks at 4 °C. As the last step, the ability of the aptasensor to detect chlorpyrifos in actual samples was evaluated by testing it on banana and grape extracts. As a result, the device demonstrated sufficient recovery rates, which indicate that it can find application in the food industry.

Wearable Triboelectric Nanogenerator from Waste Materials for Autonomous Information Transmission via Morse Code.

Electronic waste produced by plastic, toxic, and semiconducting components of existing electronic devices is dramatically increasing environmental pollution. To overcome these issues, the use of eco-friendly materials for designing such devices is attaining much attention. This current work presents a recycled material-based triboelectric nanogenerator (TENG) made of plastic waste and carbon-coated paper wipes (C@PWs), in which the PWs are also collected from a waste bin. The resultant C@PW-based TENG is then used for powering low-power electronic devices and, later, to generate a Morse code from a wearable for autonomous communication. In this application, the end users decode the Morse code from a customized LabVIEW program and read the transmitted signal. With further redesigning, a 9-segment keyboard is developed using nine-TENGs, connected to an Arduino controller to display the 9-segment actuation on a computer screen. Based on the above analysis, our C@PW-TENG device is expected to have an impact on future self-powered sensors and internet of things systems.

Flexible Screen-Printed Electrochemical Sensors Functionalized with Electrodeposited Copper for Nitrate Detection in Water.

Nitrate (NO3 -) contamination is becoming a major concern due to the negative effects of an excessive NO3 - presence in water which can have detrimental effects on human health. Sensitive, real-time, low-cost, and portable measurement systems able to detect extremely low concentrations of NO3 - in water are thus becoming extremely important. In this work, we present a novel method to realize a low-cost and easy to fabricate amperometric sensor capable of detecting small concentrations of NO3 - in real water samples. The novel fabrication technique combines printing of a silver (Ag) working electrode with subsequent modification of the electrode with electrodeposited copper (Cu) nanoclusters. The process was tuned in order to reach optimized sensor response, with a high catalytic activity toward electroreduction of NO3 - (sensitivity: 19.578 µA/mM), as well as a low limit of detection (LOD: 0.207 nM or 0.012 µg/L) and a good dynamic linear concentration range (0.05 to 5 mM or 31 to 310 mg/L). The sensors were tested against possible interference analytes (NO2 -, Cl-, SO4 2-, HCO3 -, CH3COO-, Fe2+, Fe3+, Mn2+, Na+, and Cu2+) yielding only negligible effects [maximum standard deviation (SD) was 3.9 µA]. The proposed sensors were also used to detect NO3 - in real samples, including tap and river water, through the standard addition method, and the results were compared with the outcomes of high-performance liquid chromatography (HPLC). Temperature stability (maximum SD 3.09 µA), stability over time (maximum SD 3.69 µA), reproducibility (maximum SD 3.20 µA), and repeatability (maximum two-time useable) of this sensor were also investigated.

Supervised binary classification methods for strawberry ripeness discrimination from bioimpedance data.

Strawberry is one of the most popular fruits in the market. To meet the demanding consumer and market quality standards, there is a strong need for an on-site, accurate and reliable grading system during the whole harvesting process. In this work, a total of 923 strawberry fruit were measured directly on-plant at different ripening stages by means of bioimpedance data, collected at frequencies between 20 Hz and 300 kHz. The fruit batch was then splitted in 2 classes (i.e. ripe and unripe) based on surface color data. Starting from these data, six of the most commonly used supervised machine learning classification techniques, i.e. Logistic Regression (LR), Binary Decision Trees (DT), Naive Bayes Classifiers (NBC), K-Nearest Neighbors (KNN), Support Vector Machine (SVM) and Multi-Layer Perceptron Networks (MLP), were employed, optimized, tested and compared in view of their performance in predicting the strawberry fruit ripening stage. Such models were trained to develop a complete feature selection and optimization pipeline, not yet available for bioimpedance data analysis of fruit. The classification results highlighted that, among all the tested methods, MLP networks had the best performances on the test set, with 0.72, 0.82 and 0.73 for the F[Formula: see text], F[Formula: see text] and F[Formula: see text]-score, respectively, and improved the training results, showing good generalization capability, adapting well to new, previously unseen data. Consequently, the MLP models, trained with bioimpedance data, are a promising alternative for real-time estimation of strawberry ripeness directly on-field, which could be a potential application technique for evaluating the harvesting time management for farmers and producers.

Optimization of a Low-Power Chemoresistive Gas Sensor: Predictive Thermal Modelling and Mechanical Failure Analysis.

The substrate plays a key role in chemoresistive gas sensors. It acts as mechanical support for the sensing material, hosts the heating element and, also, aids the sensing material in signal transduction. In recent years, a significant improvement in the substrate production process has been achieved, thanks to the advances in micro- and nanofabrication for micro-electro-mechanical system (MEMS) technologies. In addition, the use of innovative materials and smaller low-power consumption silicon microheaters led to the development of high-performance gas sensors. Various heater layouts were investigated to optimize the temperature distribution on the membrane, and a suspended membrane configuration was exploited to avoid heat loss by conduction through the silicon bulk. However, there is a lack of comprehensive studies focused on predictive models for the optimization of the thermal and mechanical properties of a microheater. In this work, three microheater layouts in three membrane sizes were developed using the microfabrication process. The performance of these devices was evaluated to predict their thermal and mechanical behaviors by using both experimental and theoretical approaches. Finally, a statistical method was employed to cross-correlate the thermal predictive model and the mechanical failure analysis, aiming at microheater design optimization for gas-sensing applications.

Laser-Induced Graphene Electrodes Modified with a Molecularly Imprinted Polymer for Detection of Tetracycline in Milk and Meat.

Tetracycline (TC) is a widely known antibiotic used worldwide to treat animals. Its residues in animal-origin foods cause adverse health effects to consumers. Low-cost and real-time measuring systems of TC in food samples are, therefore, extremely needed. In this work, a three-electrode sensitive and label-free sensor was developed to detect TC residues from milk and meat extract samples, using CO2 laser-induced graphene (LIG) electrodes modified with gold nanoparticles (AuNPs) and a molecularly imprinted polymer (MIP) used as a synthetic biorecognition element. LIG was patterned on a polyimide (PI) substrate, reaching a minimum sheet resistance (Rsh) of 17.27 ± 1.04 Ω/sq. The o-phenylenediamine (oPD) monomer and TC template were electropolymerized on the surface of the LIG working electrode to form the MIP. Surface morphology and electrochemical techniques were used to characterize the formation of LIG and to confirm each modification step. The sensitivity of the sensor was evaluated by differential pulse voltammetry (DPV), leading to a limit of detection (LOD) of 0.32 nM, 0.85 nM, and 0.80 nM in buffer, milk, and meat extract samples, respectively, with a working range of 5 nM to 500 nM and a linear response range between 10 nM to 300 nM. The sensor showed good LOD (0.32 nM), reproducibility, and stability, and it can be used as an alternative system to detect TC from animal-origin food products.

Flexible Screen Printed Aptasensor for Rapid Detection of Furaneol: A Comparison of CNTs and AgNPs Effect on Aptasensor Performance.

Furaneol is a widely used flavoring agent, which can be naturally found in different products, such as strawberries or thermally processed foods. This is why it is extremely important to detect furaneol in the food industry using ultra-sensitive, stable, and selective sensors. In this context, electrochemical biosensors are particularly attractive as they provide a cheap and reliable alternative measurement device. Carbon nanotubes (CNTs) and silver nanoparticles (AgNPs) have been extensively investigated as suitable materials to effectively increase the sensitivity of the biosensors. However, a comparison of the performance of biosensors employing CNTs and AgNPs is still missing. Herein, the effect of CNTs and AgNPs on the biosensor performance has been thoughtfully analyzed. Therefore, disposable flexible and screen printed electrochemical aptasensor modified with CNTs (CNT-ME), or AgNPs (AgNP-ME) have been developed. Under optimized conditions, CNT-MEs showed better performance compared to AgNP-ME, yielding a linear range of detection over a dynamic concentration range of 1 fM-35 µM and 2 pM-200 nM, respectively, as well as high selectivity towards furaneol. Finally, our aptasensor was tested in a real sample (strawberry) and validated with high-performance liquid chromatography (HPLC), showing that it could find an application in the food industry.

Flexible and Printed Electrochemical Immunosensor Coated with Oxygen Plasma Treated SWCNTs for Histamine Detection.

Heterocyclic amine histamine is a well-known foodborne toxicant (mostly linked to "scombroid poisoning") synthesized from the microbial decarboxylation of amino acid histidine. In this work, we report the fabrication of a flexible screen-printed immunosensor based on a silver electrode coated with single-walled carbon nanotubes (SWCNTs) for the detection of histamine directly in fish samples. Biosensors were realized by first spray depositing SWCNTs on the working electrodes and by subsequently treating them with oxygen plasma to reduce the unwanted effects related to their hydrophobicity. Next, anti-histamine antibodies were directly immobilized on the treated SWCNTs. Histamine was detected using the typical reaction of histamine and histamine-labeled with horseradish peroxidase (HRP) competing to bind with anti-histamine antibodies. The developed immunosensor shows a wide linear detection range from 0.005 to 50 ng/mL for histamine samples, with a coefficient of determination as high as 98.05%. Average recoveries in fish samples were observed from 96.00% to 104.7%. The biosensor also shows good selectivity (less than 3% relative response for cadaverine, putrescine, and tyramine), reproducibility, mechanical and time stability, being a promising analytical tool for the analysis of histamine, as well as of other food hazards.

Development of Flexible Dispense-Printed Electrochemical Immunosensor for Aflatoxin M1 Detection in Milk.

Detection of mycotoxins, especially aflatoxin M1 (AFM1), in milk is crucial to be able to guarantee food quality and safety. In recent years, biosensors have been emerging as a fast, reliable and low-cost technique for the detection of this toxin. In this work, flexible biosensors were fabricated using dispense-printed electrodes, which were functionalized with single-walled carbon nanotubes (SWCNTs) and subsequently coated with specific antibodies to improve their sensitivity. Next, the immunosensor was tested for the detection of AFM1 in buffer solution and a spiked milk sample using a chronoamperometric technique. Results showed that the working range of the sensors was 0.01 µg/L at minimum and 1 µg/L at maximum in both buffer and spiked milk. The lower limit of detection of the SWCNT-functionalized sensor was 0.02 µg/L, which indicates an improved sensitivity compared to the sensors reported so far. The sensitivity and detection range were in accordance with the limitation values imposed by regulations on milk and its products. Therefore, considering the low fabrication cost, the ease of operation, and the rapid read-out, the use of this sensor could contribute to safeguarding consumers' health.

Buckled Thin-Film Transistors and Circuits on Soft Elastomers for Stretchable Electronics.

Although recent progress in the field of flexible electronics has allowed the realization of biocompatible and conformable electronics, systematic approaches which combine high bendability (<3 mm bending radius), high stretchability (>3-4%), and low complexity in the fabrication process are still missing. Here, we show a technique to induce randomly oriented and customized wrinkles on the surface of a biocompatible elastomeric substrate, where Thin-Film Transistors (TFTs) and circuits (inverter and logic NAND gates) based on amorphous-IGZO are fabricated. By tuning the wavelength and the amplitude of the wrinkles, the devices are fully operational while bent to 13 µm bending radii as well as while stretched up to 5%, keeping unchanged electrical properties. Moreover, a flexible rectifier is also realized, showing no degradation in the performances while flat or wrapped on an artificial human wrist. As proof of concept, transparent TFTs are also fabricated, presenting comparable electrical performances to the nontransparent ones. The extension of the buckling approach from our TFTs to circuits demonstrates the scalability of the process, prospecting applications in wireless stretchable electronics to be worn or implanted.

Biomimetic Microelectronics for Regenerative Neuronal Cuff Implants.

Smart biomimetics, a unique class of devices combining the mechanical adaptivity of soft actuators with the imperceptibility of microelectronics, is introduced. Due to their inherent ability to self-assemble, biomimetic microelectronics can firmly yet gently attach to an inorganic or biological tissue enabling enclosure of, for example, nervous fibers, or guide the growth of neuronal cells during regeneration.

Design and simulation of a 800 Mbit/s data link for magnetic resonance imaging wearables.

This paper presents the optimization of electronic circuitry for operation in the harsh electro magnetic (EM) environment during a magnetic resonance imaging (MRI) scan. As demonstrator, a device small enough to be worn during the scan is optimized. Based on finite element method (FEM) simulations, the induced current densities due to magnetic field changes of 200 T s(-1) were reduced from 1 × 10(10) A m(-2) by one order of magnitude, predicting error-free operation of the 1.8V logic employed. The simulations were validated using a bit error rate test, which showed no bit errors during a MRI scan sequence. Therefore, neither the logic, nor the utilized 800 Mbit s(-1) low voltage differential swing (LVDS) data link of the optimized wearable device were significantly influenced by the EM interference. Next, the influence of ferro-magnetic components on the static magnetic field and consequently the image quality was simulated showing a MRI image loss with approximately 2 cm radius around a commercial integrated circuit of 1×1 cm(2). This was successively validated by a conventional MRI scan.

Wafer-scale design of lightweight and transparent electronics that wraps around hairs.

Electronics on very thin substrates have shown remarkable bendability, conformability and lightness, which are important attributes for biological tissues sensing, wearable or implantable devices. Here we propose a wafer-scale process scheme to realize ultra flexible, lightweight and transparent electronics on top of a 1-µm thick parylene film that is released from the carrier substrate after the dissolution in water of a polyvinyl- alcohol layer. The thin substrate ensures extreme flexibility, which is demonstrated by transistors that continue to work when wrapped around human hairs. In parallel, the use of amorphous oxide semiconductor and high-K dielectric enables the realization of analogue amplifiers operating at 12 V and above 1 MHz. Electronics can be transferred on any object, surface and on biological tissues like human skin and plant leaves. We foresee a potential application as smart contact lenses, covered with light, transparent and flexible devices, which could serve to monitor intraocular pressure for glaucoma disease.

High performance flexible electronics for biomedical devices.

Plastic electronics is soft, deformable and lightweight and it is suitable for the realization of devices which can form an intimate interface with the body, be implanted or integrated into textile for wearable and biomedical applications. Here, we present flexible electronics based on amorphous oxide semiconductors (a-IGZO) whose performance can achieve MHz frequency even when bent around hair. We developed an assembly technique to integrate complex electronic functionalities into textile while preserving the softness of the garment. All this and further developments can open up new opportunities in health monitoring, biotechnology and telemedicine.