An Electroanalytical Enzymeless α-Fe2O3-ZnO Hybrid Nanostructure-Based Sensor for Sensitive Quantification of Nitrite Ions.

Nitrite monitoring serves as a fundamental practice for protecting public health, preserving environmental quality, ensuring food safety, maintaining industrial safety standards, and optimizing agricultural practices. Although many nitrite sensing methods have been recently developed, the quantification of nitrite remains challenging due to sensitivity and selectivity limitations. In this context, we present the fabrication of enzymeless iron oxide nanoparticle-modified zinc oxide nanorod (α-Fe2O3-ZnO NR) hybrid nanostructure-based nitrite sensor fabrication. The α-Fe2O3-ZnO NR hybrid nanostructure was synthesized using a two-step hydrothermal method and characterized in detail utilizing x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). These analyses confirm the successful synthesis of an α-Fe2O3-ZnO NR hybrid nanostructure, highlighting its morphology, purity, crystallinity, and elemental constituents. The α-Fe2O3-ZnO NR hybrid nanostructure was used to modify the SPCE (screen-printed carbon electrode) for enzymeless nitrite sensor fabrication. The voltammetric methods (i.e., cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) were employed to explore the electrochemical characteristics of α-Fe2O3-ZnO NR/SPCE sensors for nitrite. Upon examination of the sensor's electrochemical behavior across a range of nitrite concentrations (0 to 500 µM), it is evident that the α-Fe2O3-ZnO NR hybrid nanostructure shows an increased response with increasing nitrite concentration. The sensor demonstrates a linear response to nitrite concentrations up to 400 µM, a remarkable sensitivity of 18.10 µA µM-1 cm-2, and a notably low detection threshold of 0.16 µM. Furthermore, its exceptional selectivity, stability, and reproducibility make it an ideal tool for accurately measuring nitrite levels in serum, yielding reliable outcomes. This advancement heralds a significant step forward in the field of environmental monitoring, offering a potent solution for the precise assessment of nitrite pollution.

Highly Sensitive Electrochemical Non-Enzymatic Uric Acid Sensor Based on Cobalt Oxide Puffy Balls-like Nanostructure.

Early-stage uric acid (UA) abnormality detection is crucial for a healthy human. With the evolution of nanoscience, metal oxide nanostructure-based sensors have become a potential candidate for health monitoring due to their low-cost, easy-to-handle, and portability. Herein, we demonstrate the synthesis of puffy balls-like cobalt oxide nanostructure using a hydrothermal method and utilize them to modify the working electrode for non-enzymatic electrochemical sensor fabrication. The non-enzymatic electrochemical sensor was utilized for UA determination using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The puffy balls-shaped cobalt oxide nanostructure-modified glassy carbon (GC) electrode exhibited excellent electro-catalytic activity during UA detection. Interestingly, when we compared the sensitivity of non-enzymatic electrochemical UA sensors, the DPV technique resulted in high sensitivity (2158 µA/mM.cm2) compared to the CV technique (sensitivity = 307 µA/mM.cm2). The developed non-enzymatic electrochemical UA sensor showed good selectivity, stability, reproducibility, and applicability in the human serum. Moreover, this study indicates that the puffy balls-shaped cobalt oxide nanostructure can be utilized as electrode material for designing (bio)sensors to detect a specific analyte.

Electrochemical Ultrasensitive Sensing of Uric Acid on Non-Enzymatic Porous Cobalt Oxide Nanosheets-Based Sensor.

Transition metal oxide (TMO)-based nanomaterials are effectively utilized to fabricate clinically useful ultra-sensitive sensors. Different nanostructured nanomaterials of TMO have attracted a lot of interest from researchers for diverse applications. Herein, we utilized a hydrothermal method to develop porous nanosheets of cobalt oxide. This synthesis method is simple and low temperature-based. The morphology of the porous nanosheets like cobalt oxide was investigated in detail using FESEM and TEM. The morphological investigation confirmed the successful formation of the porous nanosheet-like nanostructure. The crystal characteristic of porous cobalt oxide nanosheets was evaluated by XRD analysis, which confirmed the crystallinity of as-synthesized cobalt oxide nanosheets. The uric acid sensor fabrication involves the fixing of porous cobalt oxide nanosheets onto the GCE (glassy carbon electrode). The non-enzymatic electrochemical sensing was measured using CV and DPV analysis. The application of DPV technique during electrochemical testing for uric acid resulted in ultra-high sensitivity (3566.5 µAmM-1cm-2), which is ~7.58 times better than CV-based sensitivity (470.4 µAmM-1cm-2). Additionally, uric acid sensors were tested for their selectivity and storage ability. The applicability of the uric acid sensors was tested in the serum sample through standard addition and recovery of known uric acid concentration. This ultrasensitive nature of porous cobalt oxide nanosheets could be utilized to realize the sensing of other biomolecules.

Vertically Oriented Zinc Oxide Nanorod-Based Electrolyte-Gated Field-Effect Transistor for High-Performance Glucose Sensing.

Nanomaterial-based biosensors are a promising fit for portable and field-deployable diagnosis sensor devices due to their mass production, miniaturization, and integration capabilities. However, the fabrication of highly stable and reproducible biosensor devices is challenging. In this work, we grow a vertically oriented architecture of zinc oxide nanorods onto the active working area (i.e., the channel between the source and drain) of a field-effect transistor (FET) using a low-temperature hydrothermal method. The glucose oxidase enzyme was immobilized on the zinc oxide nanorod surface by a physical adsorption method to fabricate the electrolyte-gated FET-based glucose biosensor. The electrical properties of the electrolyte-gated FET biosensor were measured with different glucose concentrations. We found a linear increase in current up to 80 mM glucose concentration with high sensitivity (74.78 µA/mMcm2) and a low detection limit (∼0.05 mM). We illustrate a highly reproducible fabrication process of zinc oxide nanorod-based FETs, where vertically grown nanorods with a higher surface-to-volume ratio enhance the enzyme immobilization, provide a microenvironment for longer enzyme activity, and translate to better glucose sensing parameters. Additionally, our electrolyte-gated FET biosensor showed promising application in freshly drawn mouse blood samples. These findings suggest a great opportunity to translate into practical high-performance biosensors for a broad range of analytes.

A fast and label-free detection of hydroxymethylated DNA using a nozzle-jet printed AuNPs@Ti3C2 MXene-based electrochemical sensor.

5-hydroxymethylcytosine (5hmC) is a key epigenetic mark in the mammalian genome that has been proposed as a promising cancer biomarker with diagnostic and prognostic potentials. A new type of two-dimensional (2D) material called MXene includes transition metal carbides and nitrides and possesses unique physico-chemical properties suitable for diverse applications, including electrochemical sensors. Here, we report a new nozzle-jet printed electrochemical sensor using gold nanoparticles (AuNPs)@Ti3C2 MXene nanocomposite for the real-time and label-free detection of 5hmC in the genome. We utilized Ti3C2 MXene as a platform to immobilize AuNPs, which have been shown to exhibit different affinity interactions toward 5-methylcytosine (5 mC) and 5hmC, and thus produce distinct electrochemical responses. To fabricate the electrode, a highly conductive and adhesive silver ink was prepared to generate a silver line onto polyethylene terephthalate (PET) substrate using nozzle-jet printing, followed by deposition of AuNPs@Ti3C2 MXene ink at one end via dropcasting. Analyses of morphology and chemical composition showed that all steps of the sensor fabrication were successful. The fabricated sensor coupled with cyclic voltammetry showed excellent performance in distinguishing 5 mC- or 5hmC-enriched cellular genomic DNAs. As a proof-of-concept investigation, we confirmed that our sensor readily and consistently detected 5hmC diminution in multiple tumors, compared to the paired normal tissues. Thus, our simple and cost-effective sensing strategy using printable AuNPs@Ti3C2 MXene ink holds promise for a wide range of practical applications in epigenetic studies as well as clinical settings.

Bioinspired cell-in-shell systems in biomedical engineering and beyond: Comparative overview and prospects.

With the development in tissue engineering, cell transplantation, and genetic technologies, living cells have become an important therapeutic tool in clinical medical care. For various cell-based technologies including cell therapy and cell-based sensors in addition to fundamental studies on single-cell biology, the cytoprotection of individual living cells is a prerequisite to extend cell storage life or deliver cells from one place to another, resisting various external stresses. Nature has evolved a biological defense mechanism to preserve their species under unfavorable conditions by forming a hard and protective armor. Particularly, plant seeds covered with seed coat turn into a dormant state against stressful environments, due to mechanical and water/gas constraints imposed by hard seed coat. However, when the environmental conditions become hospitable to seeds, seed coat is ruptured, initiating seed germination. This seed dormancy and germination mechanism has inspired various approaches that artificially induce cell sporulation via chemically encapsulating individual living cells within a thin but tough shell forming a 3D "cell-in-shell" structure. Herein, the recent advance of cell encapsulation strategies along with the potential advantages of the 3D "cell-in-shell" system is reviewed. Diverse coating materials including polymeric shells and hybrid shells on different types of cells ranging from microbes to mammalian cells will be discussed in terms of enhanced cytoprotective ability, control of division, chemical functionalization, and on-demand shell degradation. Finally, current and potential applications of "cell-in-shell" systems for cell-based technologies with remaining challenges will be explored.

Nozzle-Jet-Printed Silver/Graphene Composite-Based Field-Effect Transistor Sensor for Phosphate Ion Detection.

High concentration of dissolved phosphate ions is the main responsible factor for eutrophication of natural water bodies. Therefore, detection of phosphate ions is essential for evaluating water eutrophication. There is a need at large-scale production of real-time monitoring technology to detect phosphorus accurately. In this study, facile enzymeless phosphate ion detection is reported using a nozzle-jet-printed silver/reduced graphene oxide (Ag/rGO) composite-based field-effect transistor sensor on flexible and disposable polymer substrates. The sensor exhibits promising results in low concentration as well as real-time phosphate ion detection. The sensor shows excellent performance with a wide linear range of 0.005-6.00 mM, high sensitivity of 62.2 µA/cm2/mM, and low detection limit of 0.2 µM. This facile combined technology readily facilitates the phosphate ion detection with high performance, long-term stability, excellent reproducibility, and good selectivity in the presence of other interfering anions. The sensor fabrication method and phosphate detection technique yield low-cost, user-friendly sensing devices with less analyte consumption, which are easy to fabricate on polymer substrates on a large scale. Besides, the sensor has the capability to sense phosphate ions in real water samples, which makes it applicable in environmental monitoring.

Fabrication of a solution-gated transistor based on valinomycin modified iron oxide nanoparticles decorated zinc oxide nanorods for potassium detection.

There are considerable interests to detect and monitor the abnormal level of minerals in water for avoiding/preventing any toxic effects after consumption. Herein, we report the fabrication of solution-gated field-effect-transistor (FET) based potassium sensor using iron oxide nanoparticles (Fe2O3 NPs) modified directly grown zinc oxide nanorods (ZnO NRs). The Fe2O3 NPs modification of ZnO NRs provided stability to nanorods surface and improved surface area for valinomycin immobilization. As-fabricated potassium sensor (valinomycin-Fe2O3 NPs-ZnO NRs/SiO2/Si) provided enhanced current response with increasing potassium concentration. During sensing measurements, FET sensor showed high sensitivity (4.65 µA/µM/cm2) in the linear range of 0.1 µM to 125 µM, low limit of detection (∼0.04 µM), good stability, excellent reproducibility, and favorable selectivity. Thus, good sensing performance of the FET based potassium sensor presents it as simple, low-cost, and convenient device for selective detection of potassium in solution.

Fully nozzle-jet printed non-enzymatic electrode for biosensing application.

The progress in developing the electrochemical sensors for biomolecule detection requires a facile device fabrication method. Herein, we report printing of silver (Ag) precursor and copper oxide nanoparticles (CuO NPs) inks by nozzle-jet technique to fabricate non-enzymatic glucose biosensor on flexible polyethylene terephthalate (PET) substrate. The fully printed CuO NPs/Ag/PET electrodes were characterized using electrochemical techniques for non-enzymatic biosensing of glucose. The fully printed non-enzymatic biosensor exhibited a high sensitivity (1424.2 µA mM-1 cm-2), linear range from 0.1 to 15 mM, low detection limit (0.3 µM; S/N = 3) and fast response time of ∼2 s under a working potential of +0.6 V. Additionally, printed electrodes demonstrated an excellent long term stability, high reproducibility, good selectivity and high accuracy during glucose concentration measurements in human blood and serum samples. These results indicate that the electrode fabrication using nozzle-jet printing can be regarded as a potential technique for the future development of high performance and low cost bio/chemical sensor devices.

Nozzle-jet printed flexible field-effect transistor biosensor for high performance glucose detection.

Printable electronics is a subject of great interest for low-cost, facile and environmentally-friendly large scale device production. But, it still remains challenging for printable biosensor development. Herein, we present the fabrication of nozzle-jet printed flexible field-effect transistor (FET) glucose biosensor. The silver source-drain electrodes and ZnO seed layers were printed on flexible substrate by nozzle-jet printer followed by ZnO nanorods (ZnO NRs) synthesis and glucose oxidase (GOx) immobilization. Utilization of nozzle-jet printing methods resulted in highly reproducible electrodes with well-defined vertical grown ZnO NRs for high GOx loading and enhanced glucose sensing performance in a wide glucose detection range. The stability, anti-interference ability, reproducibility, reusability, and applicability in human serum samples were also assessed. Overall, biosensor fabrication using nozzle-jet printer will not only provide large scale production of highly reproducible electrodes but also reduce the fabrication cost. Additionally, printed electrodes can be modified accordingly for different analyte detection.

Highly Efficient Non-Enzymatic Glucose Sensor Based on CuO Modified Vertically-Grown ZnO Nanorods on Electrode.

There is a major challenge to attach nanostructures on to the electrode surface while retaining their engineered morphology, high surface area, physiochemical features for promising sensing applications. In this study, we have grown vertically-aligned ZnO nanorods (NRs) on fluorine doped tin oxide (FTO) electrodes and decorated with CuO to achieve high-performance non-enzymatic glucose sensor. This unique CuO-ZnO NRs hybrid provides large surface area and an easy substrate penetrable structure facilitating enhanced electrochemical features towards glucose oxidation. As a result, fabricated electrodes exhibit high sensitivity (2961.7 µA mM-1 cm-2), linear range up to 8.45 mM, low limit of detection (0.40 µM), and short response time (<2 s), along with excellent reproducibility, repeatability, stability, selectivity, and applicability for glucose detection in human serum samples. Circumventing, the outstanding performance originating from CuO modified ZnO NRs acts as an efficient electrocatalyst for glucose detection and as well, provides new prospects to biomolecules detecting device fabrication.