Conducting polymer nanowires for multi-analyte chemiresistive sensing

A conducting polymer nanowire-based chemiresistive sensor array was developed for the liquid-phase multi-analyte detection. The ability to distinguish and quantify multiple chemical species with a single sensory device can be useful in many areas including food industry, pollution control, biosensors, and explosives detection. A polyaniline nanowire is a good candidate for use as a chemiresistive sensing material due to its large resistivity change and ease of synthesis. However the two most important issues in chemiresistive sensors are the reproducibility in sensing and the selectivity in chemical species. For improving the reproducibility in polyaniline-based chemiresistive sensing, a self-calibration mechanism was proposed. This method utilizes two unique properties of polyaniline: one is the rate of the conductivity decay upon repeated cycling of the electrochemical potential, and the other is the position of the second redox potential, both of which are pH-dependent. These two properties were minimally affected by the polyaniline’s inherent limitations, i.e. hysteresis and degradation, and therefore were effective in obtaining repeatable measurements. In order to enhance the selectivity, a catalyst-based selective detection was proposed. This method is based on the concept that the catalytic reaction between the species and the catalysts causes a local pH change near the polyaniline nanowire network which changes the resistance of the polymer. Finally, a sensor array consisting of polyaniline nanowire-based chemiresistors with each sensing element modified with a unique catalyst was implemented for multi-analyte sensing of ascorbic acid, dopamine, and hydrogen peroxide. Principal component algorithm was applied for the classification and semi-quantification of the chemical species

Wearable Nano-Based Gas Sensors for Environmental Monitoring and Encountered Challenges in Optimization

With a rising emphasis on public safety and quality of life, there is an urgent need to ensure optimal air quality, both indoors and outdoors. Detecting toxic gaseous compounds plays a pivotal role in shaping our sustainable future. This review aims to elucidate the advancements in smart wearable (nano)sensors for monitoring harmful gaseous pollutants, such as ammonia (NH3), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), carbon monoxide (CO), carbon dioxide (CO2), hydrogen sulfide (H2S), sulfur dioxide (SO2), ozone (O3), hydrocarbons (CxHy), and hydrogen fluoride (HF). Differentiating this review from its predecessors, we shed light on the challenges faced in enhancing sensor performance and offer a deep dive into the evolution of sensing materials, wearable substrates, electrodes, and types of sensors. Noteworthy materials for robust detection systems encompass 2D nanostructures, carbon nanomaterials, conducting polymers, nanohybrids, and metal oxide semiconductors. A dedicated section dissects the significance of circuit integration, miniaturization, real-time sensing, repeatability, reusability, power efficiency, gas-sensitive material deposition, selectivity, sensitivity, stability, and response/recovery time, pinpointing gaps in the current knowledge and offering avenues for further research. To conclude, we provide insights and suggestions for the prospective trajectory of smart wearable nanosensors in addressing the extant challenges

Doctor of Philosophy

dissertationExplosives and drugs cause problems in society when used inappropriately. It is highly desired to detect these chemicals in a quick and reliable way with low cost. Vapor detection of explosives and drugs has been proven to be one of the most effective, practical, and noninvasive methods. Among all the methods developed so far, highly sensitive carbon nanotube-based (CNT-based) chemiresistive sensors remain promising. In this dissertation, we explored and developed three CNT-based sensors for the explosive and drug detection. In this dissertation, we proposed that the dominant mechanism of our oligomer-coated CNT-based sensors is due to the swelling of the oligomers. Based on this swelling mechanism, we have designed three oligomers or polymers functionalized CNT-based sensors for the detection of nitro-explosives, alkanes (related with ammonium nitrate/fuel oil), and amines (related with methamphetamine), respectively. Beyond the high sensitivity to the target analytes, the selectivity of the sensors was largely enhanced by the careful selection of oligomers and polymers. The three oligomers and polymers under investigation can enhance the interaction between the sensor and the analyte, and facilitate the dispersion of CNTs in a solution. For the detection of nitro-explosives, we chose an oligomer that had been successfully demonstrated as a fluorescence-based nitro-explosive sensing materials. For the detection of alkanes and amines, we introduced the alkane side chains and carboxylic acid functional groups in the polymer. This dissertation demonstrated three examples of oligomer or polymer functionalization CNT-based sensors for the detection of explosives and drugs. Meanwhile, the dominant mechanism of the sensors was proposed. This research paved ways for developing chemical vapor sensors with better sensitivity and selectivity in the future

Electrospun Nanofibers for Label-Free Sensor Applications

Electrospinning is a simple, low-cost and versatile method for fabricating submicron and nano size fibers. Due to their large surface area, high aspect ratio and porous structure, electrospun nanofibers can be employed in wide range of applications. Biomedical, environmental, protective clothing and sensors are just few. The latter has attracted a great deal of attention, because for biosensor application, nanofibers have several advantages over traditional sensors, including a high surface-to-volume ratio and ease of functionalization. This review provides a short overview of several electrospun nanofibers applications, with an emphasis on biosensor applications. With respect to this area, focus is placed on label-free sensors, pertaining to both recent advances and fundamental research. Here, label-free sensor properties of sensitivity, selectivity, and detection are critically evaluated. Current challenges in this area and prospective future work is also discussed

Electronic nose for analysis of volatile organic compounds in air and exhaled breath.

Exhaled breath is a complex mixture containing numerous volatile organic compounds (VOCs) at trace levels (ppb to ppt) including hydrocarbons, alcohols, ketones, aldehydes, esters and other non-volatile compounds. Different patterns of VOCs have been correlated with various diseases. The concentration levels of VOCs in exhaled breath depend on an individual subject’s health status. Therefore, breath analysis has great potential for clinical diagnostics, monitoring therapeutic progress and drug metabolic products. Even though up to 3000 compounds may be detected in breath, the matrix of exhaled breath is less complex than that of blood or other body fluids. Breath analysis can be performed on people irrespective of age, gender, lifestyle, or other confounding factors. Breath gas concentration can be related to VOC concentrations in blood via mathematical modeling; for example, as in blood alcohol testing. Since exhaled breath samples are easy to collect and online instruments are commercially available, VOC analysis in exhaled breath appears to be a promising tool for noninvasive detection and monitoring of diseases. Breath analysis has been very successful in identifying cancer, diabetes and other diseases by using a chemiresistor sensor array to detect biomarkers. The objective of this research project is to develop sensor arrays ― or so-called electronic nose ― for analysis of VOCs in air and exhaled breath. In this dissertation, we have investigated both commercial and synthesized thiol functionalized gold nanoparticles (AuNPs) as sensing materials for analysis of VOCs in air and exhaled breath. The advantages of these sensors include very high sensitivity, selectivity for detection of target analytes and operation at ambient temperature. The synthesis and material characterization of new thiols and AuNPs for increasing sensitivity and selectivity have been studied. Selected commercial thiols and in-house synthesized new functional thiols have been used to modify AuNP-based sensors for detection of VOCs in air and exhaled breath. The interdigitated electrodes (IDE) used for the sensors were fabricated by microelectromechanical systems (MEMS) microfabrication technologies. The sensor arrays were characterized by measuring the resistance difference from vacuum and different spiked analyte concentrations in air and breath samples. Air samples and breath samples were collected using Tedlar bags, and analyzed using the thiol functionalized AuNP sensors. The analysis of air samples provides a reference for analysis of exhaled breath samples. The sensors have demonstrated a low detection limit of 0.1 ppbv of acetone and ethanol in dry air and exhaled breath. The concentrations of acetone in air and exhaled breath were determined by a silicon microreactor approach. The measurements of acetone by the microreactor approach were correlated with the sensor signals. The intellectual thrust of this research is the rational design of an electronic nose for analysis of VOCs in exhaled breath, which offers a new frontier in medical diagnostics because of its non-invasive and inexpensive characteristics

Nanomaterials for Healthcare Biosensing Applications

In recent years, an increasing number of nanomaterials have been explored for their applications in biomedical diagnostics, making their applications in healthcare biosensing a rapidly evolving field. Nanomaterials introduce versatility to the sensing platforms and may even allow mobility between different detection mechanisms. The prospect of a combination of different nanomaterials allows an exploitation of their synergistic additive and novel properties for sensor development. This paper covers more than 290 research works since 2015, elaborating the diverse roles played by various nanomaterials in the biosensing field. Hence, we provide a comprehensive review of the healthcare sensing applications of nanomaterials, covering carbon allotrope-based, inorganic, and organic nanomaterials. These sensing systems are able to detect a wide variety of clinically relevant molecules, like nucleic acids, viruses, bacteria, cancer antigens, pharmaceuticals and narcotic drugs, toxins, contaminants, as well as entire cells in various sensing media, ranging from buffers to more complex environments such as urine, blood or sputum. Thus, the latest advancements reviewed in this paper hold tremendous potential for the application of nanomaterials in the early screening of diseases and point-of-care testing

Multilayer Thin Films

This book, "Multilayer Thin Films-Versatile Applications for Materials Engineering", includes thirteen chapters related to the preparations, characterizations, and applications in the modern research of materials engineering. The evaluation of nanomaterials in the form of different shapes, sizes, and volumes needed for utilization in different kinds of gadgets and devices. Since the recently developed two-dimensional carbon materials are proving to be immensely important for new configurations in the miniature scale in the modern technology, it is imperative to innovate various atomic and molecular arrangements for the modifications of structural properties

Multilayer Thin Films

This book, "Multilayer Thin Films-Versatile Applications for Materials Engineering", includes thirteen chapters related to the preparations, characterizations, and applications in the modern research of materials engineering. The evaluation of nanomaterials in the form of different shapes, sizes, and volumes needed for utilization in different kinds of gadgets and devices. Since the recently developed two-dimensional carbon materials are proving to be immensely important for new configurations in the miniature scale in the modern technology, it is imperative to innovate various atomic and molecular arrangements for the modifications of structural properties. Of late, graphene and graphene-related derivatives have been proven as the most versatile two-dimensional nanomaterials with superb mechanical, electrical, electronic, optical, and magnetic properties. To understand the in-depth technology, an effort has been made to explain the basics of nano dimensional materials. The importance of nano particles in various aspects of nano technology is clearly indicated. There is more than one chapter describing the use of nanomaterials as sensors. In this volume, an effort has been made to clarify the use of such materials from non-conductor to highly conducting species. It is expected that this book will be useful to the postgraduate and research students as this is a multidisciplinary subject

Conductive polymers for carbon dioxide sensing

Augmented levels of carbon dioxide (CO2) in greenhouses stimulate plant growth through photosynthesis. Wireless sensor networks monitoring CO2 levels in greenhouses covering large areas require preferably low power sensors to minimize energy consumption. Therefore, the main objective of this research is to develop CO2 sensors using conductive polymer/polyelectrolyte blends as low power sensing layers operating at room temperature. The transduction principle is based on a relative change in conductivity of the polymer/blend film with regard to variation in CO2 concentration. Conductive polymers including emeraldine base polyaniline (EB-PANI), sodium salt of sulfonated polyaniline(SPAN-Na) and their blends with poly(vinyl alcohol) (PVA) were investigated for CO2 sensing. Conductivity of EB-PANI did not vary in the required pH range for CO2 sensing (pH4 - pH7), however a sulfonated derivative (SPAN-Na) showed an appropriate conductivity change in this pH range. Frequency-dependent impedance of the polymer films casted on interdigitated platinum electrodes were measured. A significant decrease in impedance of the SPAN-Na:PVA blend films was observed at high CO2 concentrations (above 20,000 ppm) under high humidity. The effect of humidity on intrinsic and ionic conductivity of the polymerswas investigated by electrochemical impedance spectroscopy. In addition, polyethyleneimine (PEI) and its blends with other polyelectrolytes including SPAN-Na, poly(sodium 4-styrenesulfonate) (PSS-Na) and Nafion sodium salt (Nafion-Na) exhibited a better sensitivity over a wide range of CO2 concentrations (from 400 ppm to 10,000 ppm). Both dc resistance and ac impedance increased when the films were exposed to CO2 at high humidity. The relative change in impedance of the PEI films was about 6-12%. The response time was 4-5 min but recovery time was quite long from 20 to 60 min. A novel solution to reduce the recovery time was achieved with PEI blends. The blend of PEI:SPAN-Na exhibited a fast response (1.5-4 min) and a short recovery time (1.5-10 min) but a reduced sensitivity in comparison with pure PEI. Furthermore, blends of PEI with PSS-Na, Nafion-Na gave a good sensitivity (up to 2-3 order improvement) and relatively short recovery time (10-20 min). The interactions between sulfonate groups with amine groups of PEI might explain the higher CO2 sensitivity of this PEI blend. Some perspectives are sketched for polymer sensors to be applied in wireless sensor network for greenhouses and other potential applications.</p

Electrical and Electro-Optical Biosensors

Electrical and electro-optical biosensing technologies are critical to the development of innovative POCT devices, which can be used by both professional and untrained personnel for the provision of necessary health information within a short time for medical decisions to be determined, being especially important in an era of global pandemics. This Special Issue includes a few pioneering works concerning biosensors utilizing electrochemical impedance, localized surface plasmon resonance, and the bioelectricity of sensing materials in which the amount of analyte is pertinent to the signal response. The presented results demonstrate the potential of these label-free biosensing approaches in the detection of disease-related small-molecule metabolites, proteins, and whole-cell entities