High performance nonenzymatic electrochemical sensors via thermally grown Cu native oxides (CuNOx) towards sweat glucose monitoring.

Diabetes, which is the seventh leading cause of death globally, necessitates real-time blood glucose monitoring, a process that is often invasive. A promising alternative is sweat glucose monitoring, which typically uses transition metals and their oxide nanomaterials as sensors. Despite their excellent surface-to-volume ratio, these materials have some drawbacks, including poor conductivity, structural collapse, and aggregation. As a result, selecting highly electroconductive materials and optimizing their nanostructures is critical. In this work, we developed a high-performance, low-cost, nonenzymatic sensor for sweat glucose detection, using the thermally grown native oxide of copper (CuNOx). By heating Cu foil at 160, 250, and 280 °C, we grew a native oxide layer of approximately 140 nm cupric oxide (CuO), which is excellent for glucose electrocatalysis. Using cyclic voltammetry, we found that our CuNOx sensors prepared at 280 °C exhibited a sensitivity of 1795 µA mM-1 cm-2, a linear range up to the desired limit of 1.00 mM for sweat glucose with excellent linearity (R2 = 0.9844), and a lower limit of detection of 135.39 µM. For glucose sensing, the redox couple Cu(II)/Cu(III) oxidizes glucose to gluconolactone and subsequently to gluconic acid, producing an oxidation current in an alkaline environment. Our sensors showed excellent repeatability and stability (remaining stable for over a year) with a relative standard deviation (RSD) of 2.48% and 4.17%, respectively, for 1 mM glucose. The selectivity, when tested with common interferants found in human sweat and blood, showed an RSD of 4.32%. We hope that the electrocatalytic efficacy of the thermally grown CuNOx sensors for glucose sensing can introduce new avenues in the fabrication of sweat glucose sensors.

Electrochemical Sensing of Lead in Drinking Water Using Copper Foil Bonded with Polymer.

Levels of lead (Pb) in tap water that are well below established guidelines are now considered harmful, so the detection of sub-parts-per-billion (ppb) Pb levels is crucial. In this work, we developed a two-step, facile, and inexpensive fabrication approach that involves direct bonding of copper (Cu) and liquid crystal polymer (LCP) followed by polyester resin printing for masking onto Cu/LCP to fabricate Cu thin-film-based Pb sensors. The oxygen plasma-treated surfaces resulted in strongly bonded Cu/LCP with a high peel strength of 500 N/m due to the highly hydrophilic nature of both surfaces. The bonded specimen can withstand wet etching of the electrode and can address delamination of the electrode for prolonged use in application environments. The Cu-foil-based electrochemical sensor showed sensitivity of ~11 nA/ppb/cm2 and a limit of detection (LOD) of 0.2 ppb (0.2 µg/L) Pb ions in water. The sensor required only 30 s and a 100 µL sample to detect Pb. To date, this is the most rapid detection of Pb performed using an all-Cu-based sensor. The selectivity test of Cu to Pb with interferences from cadmium and zinc showed that their peaks were separated by a few hundred millivolts. This approach has strong potential towards realizing low-cost, highly reliable integrated water quality monitoring systems.

Electrochemical sensing: A prognostic tool in the fight against COVID-19.

The COVID-19 pandemic has devastated the world, despite all efforts in infection control and treatment/vaccine development. Hospitals are currently overcrowded, with health statuses of patients often being hard to gauge. Therefore, methods for determining infection severity need to be developed so that high-risk patients can be prioritized, resources can be efficiently distributed, and fatalities can be prevented. Electrochemical prognostic biosensing of various biomarkers may hold promise in solving these problems as they are low-cost and provide timely results. Therefore, we have reviewed the literature and extracted the most promising biomarkers along with their most favourable electrochemical sensors. The biomarkers discussed in this paper are C-reactive protein (CRP), interleukins (ILs), tumour necrosis factor alpha (TNFα), interferons (IFNs), glutamate, breath pH, lymphocytes, platelets, neutrophils and D-dimer. Metabolic syndrome is also discussed as comorbidity for COVID-19 patients, as it increases infection severity and raises chances of becoming infected. Cannabinoids, especially cannabidiol (CBD), are discussed as a potential adjunct therapy for COVID-19 as their medicinal properties may be desirable in minimizing the neurodegenerative or severe inflammatory damage caused by severe COVID-19 infection. Currently, hospitals are struggling to provide adequate care; thus, point-of-care electrochemical sensor development needs to be prioritized to provide an approximate prognosis for hospital patients. During and following the immediate aftermath of the pandemic, electrochemical sensors can also be integrated into wearable and portable devices to help patients monitor recovery while returning to their daily lives. Beyond the COVID-19 pandemic, these sensors will also prove useful for monitoring inflammation-based diseases such as cancer and cardiovascular disease.

Glutamate sensing in biofluids: recent advances and research challenges of electrochemical sensors.

Glutamate is a nonessential amino acid and a putative neurotransmitter. When its consumption exceeds its synthesis, it becomes necessary to monitor its levels. Hence, a low-cost, sensitive and real-time monitoring of glutamate to quantify pain and detect neurodegenerative diseases is imperative to improve pharmacotherapy and early diagnosis for health care. While enzymatic electrochemical sensors are promising to address issues in lab-based detection techniques, non-enzymatic sensors are better due to their higher stability and lower cost. In this review, we aim to discuss the recent advances and remaining challenges of sensing glutamate in biofluids. First, we discuss the metabolic routes of glutamate, followed by its transmission processes to the biofluids. Second, we identify the connection of glutamate to pathologies as a potential biomarker. Third, we emphasize electrochemical sensors instantaneously detect glutamate in biofluids in real-time, quantifying pain and monitoring neurodegenerative diseases. The literature shows the concentration of glutamate in biofluids, such as plasma, cerebral spinal fluid, urine, and saliva are in the range of 5-100 µM, 0.5-2 µM, 8.5 (3.3-18.4) µM mM-1 creatinine, and 0.232 ± 0.177 µM respectively. While these concentration levels are sometimes lower than the detection limit of electrochemical sensors, functionalization of the nanomaterials currently being used such as NiO and Co3O4 with carbon nanotubes or beta-cyclodextrin may improve the sensing performance. Another key challenge in the research is to develop relationships between glutamate and biofluids. Finally, we have to advance electrochemical sensors that are compatible to detect glutamate in physiological conditions for long durations of time.

Correction: Glutamate sensing in biofluids: recent advances and research challenges of electrochemical sensors.

Correction for 'Glutamate sensing in biofluids: recent advances and research challenges of electrochemical sensors' by Jessica Schultz et al., Analyst, 2020, 145, 321-347. DOI: 10.10.1039/C9AN01609K.

Paper-Based, Hand-Drawn Free Chlorine Sensor with Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate).

The concentration of free chlorine used for disinfecting drinking water, recreational water, and food processing water is critical for environmental and human health conditions, and should be controlled within stipulated ranges. This report, for the first time, describes a paper-based electrochemical free chlorine sensor fabricated by hand-drawing. The electrical resistivity of a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) chemoresistor increases when it is exposed to free chlorine in water due to oxidation reactions. Because the relative change of the electrical resistance represents the sensor's response, the sensor can be fabricated by hand-drawing with different shapes and dimensions. The fabrication steps are all at room temperature, require no instrumentation or equipment, and can be carried out by untrained personnel. The fabricated sensor is mechanically stable, reusable, has a wide sensing range, and can accurately measure free chlorine concentrations in real water samples. Therefore, the low-cost, hand-drawn free chlorine sensor is of great significance for water quality monitoring in less developed areas where fabrication facilities, analytical equipment, and trained personnel are limited, but the need for analytical devices is critical. In addition to the free chlorine sensor demonstrated in this study, other types of PEDOT:PSS-based sensors and electronic devices can be fabricated by the developed hand-drawing process.

Materials analyses and electrochemical impedance of implantable metal electrodes.

Implantable electrodes with high flexibility, high mechanical fixation and low electrochemical impedance are desirable for neuromuscular activation because they provide safe, effective and stable stimulation. In this paper, we report on detailed materials and electrical analyses of three metal implantable electrodes - gold (Au), platinum (Pt) and titanium (Ti) - using X-ray photoelectron spectroscopy (XPS), scanning acoustic microscopy, drop shape analysis and electrochemical impedance spectroscopy. We investigated the cause of changes in electrochemical impedance of long-term immersed Au, Pt and Ti electrodes on liquid crystal polymers (LCPs) in phosphate buffered saline (PBS). We analyzed the surface wettability, surface and interface defects and the elemental depth profile of the electrode-adhesion layers on the LCP. The impedance of the electrodes decreased at lower frequencies, but increased at higher frequencies compared with that of the short-term immersion. The increase of impedances was influenced by the oxidation of the electrode/adhesion-layers that affected the double layer capacitance behavior of the electrode/PBS. The oxidation of the adhesion layer for all the electrodes was confirmed by XPS. Alkali ions (sodium) were adsorbed on the Au and Pt surfaces, but diffused into the Ti electrode and LCPs. The Pt electrode showed a higher sensitivity to surface and interface defects than that of Ti and Au electrodes. These findings may be useful when designing electrodes for long-term implantable devices.

Polyaniline-based bovine serum albumin imprinted electrochemical sensor for ultra-trace-level detection in clinical and food safety applications.

Monitoring bovine serum albumin (BSA) at ultra-low levels is crucial for clinical and food safety applications, as it plays a significant role in identifying various health conditions and potential risks, necessitating fast, trace-level detection of BSA. This study proposes an approach to address these challenges by employing molecularly imprinted polymer (MIP) to develop an ultra-trace-level and cost-effective BSA sensing platform. The MIP electrochemical sensor was developed using polyaniline (PANI) combined with the protein crosslinker glutaraldehyde (GA) to optimize BSA surface imprinting in the MIP. As a result, the sensor achieves a sensitivity of 1.24 µA/log(pg/mL), with a picomolar detectable limit of 2.3 pg/mL (0.035 pM) and a wide detection range from 20 pg/mL to 200,000 pg/mL (0.303 pM to 3030 pM), making it suitable for clinical and food safety applications. Additionally, the study explores the interaction between an acidic surfactant protein eluent (acetic acid with sodium dodecyl sulfate, AcOH-SDS) and BSA vacant sites, enhancing recognition and re-binding. The PANI-based MIP sensor demonstrates initial feasibility and practicality in commercial milk and real human serum, opening avenues for early disease detection and ensuring food safety in BSA-related immune responses.

Green synthesized gold nanoparticles and CuO-based nonenzymatic sensor for saliva glucose monitoring.

Glucose, essential for brain and muscle functions, requires careful monitoring in diabetes and other chronic disease management. While blood glucose monitoring provides precise information about these diseases, it remains an invasive method. Saliva glucose monitoring could offer an alternative approach, but the glucose concentration in saliva is very low. In this work, we report a simple, low-cost, highly sensitive nonenzymatic electrochemical glucose sensor. We developed this sensor using green synthesized gold nanoparticles (AuNPs) and wet chemical synthesized copper oxide (CuO) nanoparticles on a screen-printed carbon electrode (Au/CuO/SPCE). The sensor's high sensitivity results from dual amplification strategies using AuNPs and CuO nanomaterials, each demonstrating catalytic activity towards glucose. This shows promising potential for saliva glucose monitoring. The AuNPs were synthesized using an Au precursor and orange peel extract (OPE), yielding stable colloidal AuNPs with a mean diameter of about 37 nm, thus eliminating the need for additional capping agents. Under optimal conditions, amperometric tests revealed that the sensor responded linearly to glucose concentrations ranging from 2 µM to 397 µM with a sensitivity of 236.70 µA mM-1 cm-2. Furthermore, the sensor demonstrated excellent reproducibility, stability and high selectivity for glucose in the presence of different biomolecules. We validated the sensor's efficacy by measuring glucose in human saliva, showing its potential for noninvasive glucose monitoring. This research advances the development of point-of-care devices, positioning the sensor as a promising tool for noninvasive glucose monitoring and improved diabetes management.

Formation of gallium arsenide nanostructures in Pyrex glass.

In this paper, we report on a simple, low-cost process to grow GaAs nanostructures of a few nm diameter and ∼50 nm height in Pyrex glass wafers. These nanostructures were grown by sequential plasma activation of GaAs and Pyrex glass surfaces using a low-temperature hybrid plasma bonding technology in air. Raman analyses of the activated surfaces show gallium oxide and arsenic oxide, as well as suppressed non-bridging oxygen with aluminate and boroxol chains in glass. The flow of alkaline ions toward the cathode and the replacement of alkaline ions by Ga and As ions in glass result in the growth of GaAs nanostructures in nanopores/nanoscratches in glass. These nanopores/nanoscratches are believed to be the origin of the growth of the nanostructures. It was found that the length of the GaAs nanostructures may be controlled by an electrostatic force. Cross-sectional observation of the bonded interface using high-resolution transmission electron microscopy confirms the existence of the nanostructures. A possible application of the nanostructures in glass is a filtration system for biomolecules.

Nanomaterials-Based Electrochemical Δ9-THC and CBD Sensors for Chronic Pain.

Chronic pain is now included in the designation of chronic diseases, such as cancer, diabetes, and cardiovascular disease, which can impair quality of life and are major causes of death and disability worldwide. Pain can be treated using cannabinoids such as Δ9-tetrahydrocannabinol (Δ9-THC) and cannabidiol (CBD) due to their wide range of therapeutic benefits, particularly as sedatives, analgesics, neuroprotective agents, or anti-cancer medicines. While little is known about the pharmacokinetics of these compounds, there is increasing interest in the scientific understanding of the benefits and clinical applications of cannabinoids. In this review, we study the use of nanomaterial-based electrochemical sensing for detecting Δ9-THC and CBD. We investigate how nanomaterials can be functionalized to obtain highly sensitive and selective electrochemical sensors for detecting Δ9-THC and CBD. Additionally, we discuss the impacts of sensor pretreatment at fixed potentials and physiochemical parameters of the sensing medium, such as pH, on the electrochemical performance of Δ9-THC and CBD sensors. We believe this review will serve as a guideline for developing Δ9-THC and CBD electrochemical sensors for point-of-care applications.

Nonenzymatic Electrochemical Glutamate Sensor Using Copper Oxide Nanomaterials and Multiwall Carbon Nanotubes.

Glutamate is an important neurotransmitter due to its critical role in physiological and pathological processes. While enzymatic electrochemical sensors can selectively detect glutamate, enzymes cause instability of the sensors, thus necessitating the development of enzyme-free glutamate sensors. In this paper, we developed an ultrahigh sensitive nonenzymatic electrochemical glutamate sensor by synthesizing copper oxide (CuO) nanostructures and physically mixing them with multiwall carbon nanotubes (MWCNTs) onto a screen-printed carbon electrode. We comprehensively investigated the sensing mechanism of glutamate; the optimized sensor showed irreversible oxidation of glutamate involving one electron and one proton, and a linear response from 20 µM to 200 µM at pH 7. The limit of detection and sensitivity of the sensor were about 17.5 µM and 8500 µA·mM-1·cm-2, respectively. The enhanced sensing performance is attributed to the synergetic electrochemical activities of CuO nanostructures and MWCNTs. The sensor detected glutamate in whole blood and urine and had minimal interference with common interferents, suggesting its potential for healthcare applications.

Deep Learning-Based Metasurface Design for Smart Cooling of Spacecraft.

A reconfigurable metasurface constitutes an important block of future adaptive and smart nanophotonic applications, such as adaptive cooling in spacecraft. In this paper, we introduce a new modeling approach for the fast design of tunable and reconfigurable metasurface structures using a convolutional deep learning network. The metasurface structure is modeled as a multilayer image tensor to model material properties as image maps. We avoid the dimensionality mismatch problem using the operating wavelength as an input to the network. As a case study, we model the response of a reconfigurable absorber that employs the phase transition of vanadium dioxide in the mid-infrared spectrum. The feed-forward model is used as a surrogate model and is subsequently employed within a pattern search optimization process to design a passive adaptive cooling surface leveraging the phase transition of vanadium dioxide. The results indicate that our model delivers an accurate prediction of the metasurface response using a relatively small training dataset. The proposed patterned vanadium dioxide metasurface achieved a 28% saving in coating thickness compared to the literature while maintaining reasonable emissivity contrast at 0.43. Moreover, our design approach was able to overcome the non-uniqueness problem by generating multiple patterns that satisfy the design objectives. The proposed adaptive metasurface can potentially serve as a core block for passive spacecraft cooling applications. We also believe that our design approach can be extended to cover a wider range of applications.

Materials Perspectives of Integrated Plasmonic Biosensors.

With the growing need for portable, compact, low-cost, and efficient biosensors, plasmonic materials hold the promise to meet this need owing to their label-free sensitivity and deep light-matter interaction that can go beyond the diffraction limit of light. In this review, we shed light on the main physical aspects of plasmonic interactions, highlight mainstream and future plasmonic materials including their merits and shortcomings, describe the backbone substrates for building plasmonic biosensors, and conclude with a brief discussion of the factors affecting plasmonic biosensing mechanisms. To do so, we first observe that 2D materials such as graphene and transition metal dichalcogenides play a major role in enhancing the sensitivity of nanoparticle-based plasmonic biosensors. Then, we identify that titanium nitride is a promising candidate for integrated applications with performance comparable to that of gold. Our study highlights the emerging role of polymer substrates in the design of future wearable and point-of-care devices. Finally, we summarize some technical and economic challenges that should be addressed for the mass adoption of plasmonic biosensors. We believe this review will be a guide in advancing the implementation of plasmonics-based integrated biosensors.

Electrochemical Sensing of Cannabinoids in Biofluids: A Noninvasive Tool for Drug Detection.

Cannabinoid sensing in biofluids provides great insight into the effects of medicinal cannabis on the body. The prevalence of cannabis for pain management and illicit drug use necessitates knowledge translation in cannabinoids. In this Review, we provide an overview of the current detection methods of cannabinoids in bodily fluids emphasizing electrochemical sensing. First, we introduce cannabinoids and discuss the structure and metabolism of Δ9-THC and its metabolites in relation to blood, urine, saliva, sweat, and breath. Next, we briefly discuss lab based techniques for cannabinoids in biofluids. While these techniques are highly sensitive and specific, roadside safety requires a quick, portable, and cost-effective sensing method. These needs motivated a comprehensive review of advantages, disadvantages, and future directions for electrochemical sensing of cannabinoids. The literature shows the lowest limit of detection to be 3.3 pg of Δ9-THC/mL using electrochemical immunosensors, while electrodes fabricated with low cost methods such as screen-printing and carbon paste can detect as little as 25 and 1.26 ng of Δ9-THC/mL, respectively. Future research will include nanomaterial modified working electrodes, for simultaneous sensing of multiple cannabinoids. Additionally, there should be an emphasis on selectivity for cannabinoids in the presence of interfering compounds. Sensors should be fully integrated on biocompatible substrates with control electronics and intelligent components for wearable diagnostics. We hope this Review will prove to be the seminal work in the electrochemical sensing of cannabinoids.

Integration of Heterogeneous Materials for Wearable Sensors.

Wearable sensors are of interest for several application areas, most importantly for their potential to allow for the design of personal continuous health monitoring systems. For wearable sensors, flexibility is required and imperceptibility is desired. Wearable sensors must be robust to strain, motion, and environmental exposure. A number of different strategies have been utilized to achieve flexibility, imperceptibility, and robustness. All of these approaches require the integration of materials having a range of chemical, mechanical, and thermal properties. We have given a concise review of the range of materials that must be incorporated in wearable sensors regardless of the strategies adopted to achieve wearability. We first describe recent advances in the range of wearable sensing materials and their processing requirements and then discuss the potential routes to the integration of these heterogeneous materials.

Tailoring MWCNTs and ß-Cyclodextrin for Sensitive Detection of Acetaminophen and Estrogen.

Monitoring of trace amount of acetaminophen and estrogen in drinking water is of great importance because of their potential links to gastrointestinal diseases and breast and prostate cancers. The sensitive and accurate detection of acetaminophen and estrogen requires the development of advanced sensing materials that possess appropriate number of analyte-capturing sites and suitable signal conduction path. This can be achieved by implementing appropriate chemical attachment of multiwalled carbon nanotubes (MWCNTs) and ß-cyclodextrin (ßCD). Here, we report a systematic investigation of four types of modified MWCNT-ßCD: (1) physical mixing, (2) "click reaction", (3) thionyl chloride esterification, and (4) Steglich esterification. The Steglich esterification is a one-step approach with shorter reaction time, lower reaction temperature, and eliminates handling of air/moisture-sensitive reagents. MWCNT-ßCD prepared by Steglich esterification possessed moderate ßCD loading (5-10 wt %), large effective surface area, and fast electron transfer. The host-guest interaction of ßCD and redox properties of MWCNT enabled sensitive detection of acetaminophen and 17ß-estradiol (E2 is a primary female sex hormone) in the range of 0.005-20 and 0.01-15 µM, with low detection limits of 3.3 and 2.5 nM, respectively. We demonstrated accurate detection results of pharmaceutical compositions in water and urine samples. These results indicate that Steglich esterification method may be applied in fabricating pharmaceutical contaminants sensors for health and environmental applications.

Low-temperature solution processing of palladium/palladium oxide films and their pH sensing performance.

Highly sensitive, easy-to-fabricate, and low-cost pH sensors with small dimensions are required to monitor human bodily fluids, drinking water quality and chemical/biological processes. In this study, a low-temperature, solution-based process is developed to prepare palladium/palladium oxide (Pd/PdO) thin films for pH sensing. A precursor solution for Pd is spin coated onto pre-cleaned glass substrates and annealed at low temperature to generate Pd and PdO. The percentages of PdO at the surface and in the bulk of the electrodes are correlated to their sensing performance, which was studied by using the X-ray photoelectron spectroscope. Large amounts of PdO introduced by prolonged annealing improve the electrode's sensitivity and long-term stability. Atomic force microscopy study showed that the low-temperature annealing results in a smooth electrode surface, which contributes to a fast response. Nano-voids at the electrode surfaces were observed by scanning electron microscope, indicating a reason for the long-term degradation of the pH sensitivity. Using the optimized annealing parameters of 200°C for 48 h, a linear pH response with sensitivity of 64.71±0.56 mV/pH is obtained for pH between 2 and 12. These electrodes show a response time shorter than 18 s, hysteresis less than 8 mV and stability over 60 days. High reproducibility in the sensing performance is achieved. This low-temperature solution-processed sensing electrode shows the potential for the development of pH sensing systems on flexible substrates over a large area at low cost without using vacuum equipment.