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.

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.

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.

Aptamer-modified biosensors to visualize neurotransmitter flux.

Chemical biosensors with the capacity to continuously monitor various neurotransmitter dynamics can be powerful tools to understand complex signaling pathways in the brain. However, in vivo detection of neurochemicals is challenging for many reasons such as the rapid release and clearance of neurotransmitters in the extracellular space, or the low target analyte concentrations in a sea of interfering biomolecules. Biosensing platforms with adequate spatiotemporal resolution coupled to specific and selective receptors termed aptamers, demonstrate high potential to tackle such challenges. Herein, we review existing literature in this field. We first discuss nanoparticle-based systems, which have a simple in vitro implementation and easily interpretable results. We then examine methods employing near-infrared detection for deeper tissue imaging, hence easier translation to in vivo implementation. We conclude by reviewing live cell imaging of neurotransmitter release via aptamer-modified platforms. For each of these sensors, we discuss the associated challenges for translation to real-time in vivo neurochemical imaging. Realization of in vivo biosensors for neurotransmitters will drive future development of early prevention strategies, treatments, and therapeutics for psychiatric and neurodegenerative diseases.

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.

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.