Retraction: Polyethylene glycol-doped BiZn2VO6 as a high-efficiency solar-light-activated photocatalyst with substantial durability toward photodegradation of organic contaminations.

[This retracts the article DOI: 10.1039/C8RA06896H.].

Nanopatterned rGO/ZnO:Al seed layer for vertical growth of single ZnO nanorods.

In this work, we demonstrate a novel low-cost template-assisted route to synthesize vertical ZnO nanorod arrays on Si (100). The nanorods were grown on a patterned double seed layer comprised of reduced graphene oxide (rGO) and Al-doped ZnO nanoparticles. The seed layer was fabricated by spray-coating the substrate with graphene and then dip-coating it into a Al-doped ZnO sol-gel solution. The growth template was fabricated from a double-layer resist, spin-coated on top of the rGO/ZnO:Al seed layer, and patterned by colloidal lithography. The results show a successful chemical bath deposition of vertically aligned ZnO nanorods with controllable diameter and density in the nanoholes in the patterned resist mask. Our novel method can presumably be used to fabricate electronic devices on virtually any smooth substrate with a thermal budget of 1 min at 300 °C with the seed layer acting as a conductive strain-relieving back contact. The top contact can simply be made by depositing a suitable transparent conductive oxide or metal, depending on the specific application.

The fast nucleation/growth of Co3O4 nanowires on cotton silk: the facile development of a potentiometric uric acid biosensor.

In this study, we have used cotton silk as a source of abundant hydroxyl groups for the fast nucleation/growth of cobalt oxide (Co3O4) nanowires via a hydrothermal method. The crystal planes of the Co3O4 nanowires well matched the cubic phase. The as-synthesized Co3O4 nanowires mainly contained cobalt and oxygen elements and were found to be highly sensitive towards uric acid in 0.01 M phosphate buffer solution at pH 7.4. Importantly, the Co3O4 nanowires exhibited a large surface area, which was heavily utilized during the immobilization of the enzyme uricase via a physical adsorption method. The potentiometric response of the uricase-immobilizing Co3O4 nanowires was measured in the presence of uric acid (UA) against a silver/silver chloride (Ag/AgCl) reference electrode. The newly fabricated uric acid biosensor possessed a low limit of detection of 1.0 ± 0.2 nM with a wide linear range of 5 nM to 10 mM and sensitivity of 30.6 mV dec-1. Additionally, several related parameters of the developed uric acid biosensor were investigated, such as the repeatability, reproducibility, storage stability, selectivity, and dynamic response time, and these were found to be satisfactory. The good performance of the Co3O4 nanowires was verified based on the fast charge-transfer kinetics, as confirmed via electrochemical impedance spectroscopy. The successful practical use of the uric acid biosensor was demonstrated based on the recovery method. The observed performance of the uricase-immobilizing Co3O4 nanowires revealed that they could be considered as a promising and alternative tool for the detection of uric acid under both in vitro and in vivo conditions. Also, the use of cotton silk as a source of abundant hydroxyl groups may be considered for the remarkably fast nucleation/growth of other metal-oxide nanostructures, thereby facilitating the fabrication of functional electrochemical devices, such as batteries, water-splitting devices, and supercapacitors.

Electrochemical genosensor based on gold nanostars for the detection of Escherichia coli O157:H7 DNA.

Escherichia coli O157:H7 (E. coli O157:H7) is an enterohemorrhagic E. coli (EHEC), which has been issued as a major threat to public health worldwide due to fatal contamination of water and food. Thus, its rapid and accurate detection has tremendous importance in environmental monitoring and human health. In this regard, we report a simple and sensitive electrochemical DNA biosensor by targeting Z3276 as a genetic marker in river water. The surface of the designed gold electrode was functionalized with gold nanostars and an aminated specific sensing probe of E. coli O157:H7 to fabricate the genosensor. Cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques were applied for electrochemical characterization and detection. The synthesized gold nanostars were characterized using different characterization techniques. The fabricated DNA-based sensor exhibited a high selective ability for one, two, and three-base mismatched sequences. Regeneration, stability, selectivity, and kinetics of the bioassay were investigated. Under optimal conditions, the fabricated genosensor exhibited a linear response range of 10-5 to 10-17 µM in the standard sample and 7.3 to 1 × 10-17 µM in water samples with a low limit of quantification of 0.01 zM in water samples. The detection strategy based on silver plated gold nanostars and DNA hybridization improved the sensitivity and specificity of the assay for E. coli O157:H7 detection in real water samples without filtration. The detection assay has the advantages of high selectivity, sensitivity, low amounts of reagents, short analysis time, commercialization, and potential application for the determination of other pathogenic bacteria.

Solar-Driven Photoelectrochemical Performance of Novel ZnO/Ag2WO4/AgBr Nanorods-Based Photoelectrodes.

Highly efficient photoelectrochemical (PEC) water oxidation under solar visible light is crucial for water splitting to produce hydrogen as a source of sustainable energy. Particularly, silver-based nanomaterials are important for PEC performance due to their surface plasmon resonance which can enhance the photoelectrochemical efficiency. However, the PEC of ZnO/Ag2WO4/AgBr with enhanced visible-light water oxidation has not been studied so far. Herein, we present a novel photoelectrodes based on ZnO/Ag2WO4/AgBr nanorods (NRs) for PEC application, which is prepared by the low-temperature chemical growth method and then by successive ionic layer adsorption and reaction (SILAR) method. The synthesized photoelectrodes were investigated by several characterization techniques, emphasizing a successful synthesis of the ZnO/Ag2WO4/AgBr heterostructure NRs with excellent photocatalysis performance compared to pure ZnO NRs photoelectrode. The significantly enhanced PEC was due to improved photogeneration and transportation of electrons in the heterojunction due to the synergistic effect of the heterostructure. This study is significant for basic understanding of the photocatalytic mechanism of the heterojunction which can prompt further development of novel efficient photoelectrochemical-catalytic materials.

Synthesis of Vertically Aligned ZnO Nanorods Using Sol-gel Seeding and Colloidal Lithography Patterning.

Different ZnO nanostructures can be grown using low-cost chemical bath deposition. Although this technique is cost-efficient and flexible, the final structures are usually randomly oriented and hardly controllable in terms of homogeneity and surface density. In this work, we use colloidal lithography to pattern (100) silicon substrates to fully control the nanorods' morphology and density. Moreover, a sol-gel prepared ZnO seed layer was employed to compensate for the lattice mismatch between the silicon substrate and ZnO nanorods. The results show a successful growth of vertically aligned ZnO nanorods with controllable diameter and density in the designated openings in the patterned resist mask deposited on the seed layer. Our method can be used to fabricate optimized devices where vertically ordered ZnO nanorods of high crystalline quality are crucial for the device performance.

TiO2/ZnO Nanocomposite Material for Efficient Degradation of Methylene Blue.

In this research work, we have produced a composite material consisting titanium dioxide (TiO2) and zinc oxide (ZnO) nanostructures via precipitation method. Scanning electron microscopy (SEM) study has shown the mixture of nanostructures consisting nanorods and nano flower. Energy dispersive spectroscopy (EDS) study has confirmed the presence of Ti, Zn and O as main elements in the composite. X-ray diffraction (XRD) study has revealed that the successful presence of TiO2 and ZnO in the composite. The composite material exhibits small optical energy band gap which led to reduction of the charge recombination rate of electron-hole pairs. The band gap for the composite TiO2/ZnO samples namely 1, 2, 3 and 4 is 3.18, 3.00, 2.97 and 2.83 eV respectively. Small optical bandgap gives less relaxation time for the recombination of electron and hole pairs, thus favorable photodegradation is found. The degradation efficiency for the TiO2/ZnO samples for methylene blue in order of 55.03%, 75.7%, 85.14% and 90.08% is found for the samples 1, 2, 3 and 4 respectively. The proposed study of titanium dioxide addition into ZnO is facile and inexpensive for the development of efficient photocatalysts. This can be capitalized at large scale for the energy and.

Tin as an Effective Doping Agent into ZnO for the Improved Photodegradation of Rhodamine B.

We have fabricated ZnO nano rods by hydrothermal method and successively doped them with tin (Sn) using different concentrations of 25, 50, 75 and 100 mg of tin chloride. XRD of the fabricated structures showed that ZnO possess hexagonal wurtzite phase. Scanning electron microscopy (SEM) was used to explore the morphology and it shows nanorod like morphology for all samples and no considerable change in the structural features were found. The dimension of nanorod is 200 to 300 nm. The doped materials were then investigated for their photo catalytic degradation of environmental pollutant Rhodamine B. The performance of doped ZnO is compared with the pristine ZnO. Scanning electron microscopy (SEM) was used to explore the morphology and it shows nanorod like morphology for all samples and no considerable change in the structural features were found. The dimension of nanorod is 200 to 300 nm. XRD of the fabricated structures showed that ZnO possess hexagonal wurtzite phase. Photo catalytic activity of rhodamine B was investigated under UV light and a maximum degradation efficiency of 85% was obtained. The optical property reveals the reduction in band gap of upto 17.14% for 100 mg Sn doped ZnO. The degradation is followed by the pseudo order kinetics. The produced results are unique in terms of facile synthesis of Sn doped ZnO and excellent photo degradation efficiency, therefore these materials can be used for other environmental applications.

Gold nanomaterials for optical biosensing and bioimaging.

Gold nanoparticles (AuNPs) are highly compelling nanomaterials for biomedical studies due to their unique optical properties. By leveraging the versatile optical properties of different gold nanostructures, the performance of biosensing and biomedical imaging can be dramatically improved in terms of their sensitivity, specificity, speed, contrast, resolution and penetration depth. Here we review recent advances of optical biosensing and bioimaging techniques based on three major optical properties of AuNPs: surface plasmon resonance, surface enhanced Raman scattering and luminescence. We summarize the fabrication methods and optical properties of different types of AuNPs, highlight the emerging applications of these AuNPs for novel optical biosensors and biomedical imaging innovations, and discuss the future trends of AuNP-based optical biosensors and bioimaging as well as the challenges of implementing these techniques in preclinical and clinical investigations.

In-situ engineered MXene-TiO2/ BiVO4 hybrid as an efficient photoelectrochemical platform for sensitive detection of soluble CD44 proteins.

Interfacial charge-carrier recombination is a bottle-neck issue restricting photoelectrochemical biosensors advancement in the wearable clinical electronics. In this study, we propose a simple approach to construct a highly efficient photoactive heterojunction capable of functioning as an active substrate in PEC biosensing of CD44 proteins. Taking the advantage of high photocatalytic activity of BiVO4, and biocompatible yet conductive 2D-Ti3C2Tx nanosheets, a workable heterojunction was constructed between in-situ formed TiO2 from the partially oxidized Ti3C2Tx and lysine functionalized BiVO4 (TiO2/MX-BiVO4). The interfacial arrangement was ideal for promoting fast charge transfer from photo-excited BiVO4 and TiO2 to Ti3C2Tx, constructing an energy level-cascade that permits minimal charge-carrier recombination besides robust photocatalytic redox activity. The PEC biosensor relies on the ligand-protein interaction, where hyaluronic acid was directly immobilized over TiO2/MX-BiVO4 based on the interactions between carboxyl of lysine and amino moieties of hyaluronic acid. The PEC biosensor response depends on the inhibition in the measured photo-oxidation current of mediator species, i.e., ascorbic acid after the addition of CD44 proteins. The superior photo-activity, and robust heterojunction arrangement, produced a sensitive signal capable of recognizing CD44 in the wide concentration window of 2.2 × 10-4 ng mL-1 to 3.2 ng mL-1 with a low-detection limit of 1.4 × 10-2 pg mL-1. The strong interaction between lysine functionalized BiVO4 and hyaluronic acid enabled biosensor to exhibit robust antifouling characteristics towards similar proteins such as PSA and NSE. The quantification of CD44 protein from real-blood serum samples further confirmed the biosensor's reliability for clinical application.

Recent Progress on the Electrochemical Biosensing of Escherichia coli O157:H7: Material and Methods Overview.

Escherichia coli O157:H7 (E. coli O157:H7) is a pathogenic strain of Escherichia coli which has issued as a public health threat because of fatal contamination of food and water. Therefore, accurate detection of pathogenic E. coli is important in environmental and food quality monitoring. In spite of their advantages and high acceptance, culture-based methods, enzyme-linked immunosorbent assays (ELISAs), polymerase chain reaction (PCR), flow cytometry, ATP bioluminescence, and solid-phase cytometry have various drawbacks, including being time-consuming, requiring trained technicians and/or specific equipment, and producing biological waste. Therefore, there is necessity for affordable, rapid, and simple approaches. Electrochemical biosensors have shown great promise for rapid food- and water-borne pathogen detection. Over the last decade, various attempts have been made to develop techniques for the rapid quantification of E. coli O157:H7. This review covers the importance of E. coli O157:H7 and recent progress (from 2015 to 2020) in the development of the sensitivity and selectivity of electrochemical sensors developed for E. coli O157:H7 using different nanomaterials, labels, and electrochemical transducers.

Nanomaterial-Modified Conducting Paper: Fabrication, Properties, and Emerging Biomedical Applications.

The emerging demand for wearable, lightweight portable devices has led to the development of new materials for flexible electronics using non-rigid substrates. In this context, nanomaterial-modified conducting paper (CP) represents a new concept that utilizes paper as a functional part in various devices. Paper has drawn significant interest among the research community because it is ubiquitous, cheap, and environmentally friendly. This review provides information on the basic characteristics of paper and its functionalization with nanomaterials, methodology for device fabrication, and their various applications. It also highlights some of the exciting applications of CP in point-of-care diagnostics for biomedical applications. Furthermore, recent challenges and opportunities in paper-based devices are summarized.

In Situ Growth of CuWO4 Nanospheres over Graphene Oxide for Photoelectrochemical (PEC) Immunosensing of Clinical Biomarker.

Procalcitonin (PCT) protein has recently been identified as a clinical marker for bacterial infections based on its better sepsis sensitivity. Thus, an increased level of PCT could be linked with disease diagnosis and therapeutics. In this study, we describe the construction of the photoelectrochemical (PEC) PCT immunosensing platform based on it situ grown photo-active CuWO4 nanospheres over reduced graphene oxide layers (CuWO4@rGO). The in situ growth strategy enabled the formation of small nanospheres (diameter of 200 nm), primarily composed of tiny self-assembled CuWO4 nanoparticles (2-5 nm). The synergic coupling of CuWO4 with rGO layers constructed an excellent photo-active heterojunction for photoelectrochemical (PEC) sensing. The platform was then considered for electrocatalytic (EC) mechanism-based detection of PCT, where inhibition of the photocatalytic oxidation signal of ascorbic acid (AA), subsequent to the antibody-antigen interaction, was recorded as the primary signal response. This inhibition detection approach enabled sensitive detection of PCT in a concentration range of 10 pg·mL-1 to 50 ng.mL-1 with signal sensitivity achievable up to 0.15 pg·mL-1. The proposed PEC hybrid (CuWO4@rGO) could further be engineered to detect other clinically important species.

In-situ growth of NiWO4 saw-blade-like nanostructures and their application in photo-electrochemical (PEC) immunosensor system designed for the detection of neuron-specific enolase.

This study describes the construction of highly-sensitive photo-electrochemical (PEC) immunosensor for the detection of neuron-specific enolase (NSE). The biosensing platform is comprised of photo-active NiWO4 nanostructures, in-situ-grown over a conductive substrate (indium tin oxide) using a low-temperature template-based co-precipitation approach. The discussed approach enables the formation of discrete, yet morphologically-analogous, nanostructures with complete coverage (pinhole-free) of the electrode surface. The in-situ-grown nanostructure possess dense population with sharp saw-blade like morphological features that can support substantial immobilisation of anti-NSE agent. The constructed platform demonstrated excellent photo-catalytic activity towards uric acid (UA) which served as the base for the Electrochemical -mechanism (EC) based PEC inhibition sensing. The detection of NSE, relied on its obstruction in analytical signal observed for the photo-oxidation of UA after binding to the electrode surface via protein-antibody interaction. The constructed PEC immunosensor exhibits signal sensitivity up to 0.12 ng mL-1 of NSE with excellent signal reproducibility and electrode replicability. Moreover, the constructed platform was successfully used for NSE determination in human serum samples.

ZnO/Ag/Ag2WO4 photo-electrodes with plasmonic behavior for enhanced photoelectrochemical water oxidation.

Ag-based compounds are excellent co-catalyst that can enhance harvesting visible light and increase photo-generated charge carrier separation owing to its surface plasmon resonance (SPR) effect in photoelectrochemical (PEC) applications. However, the PEC performance of a ZnO/Ag/Ag2WO4 heterostructure with SPR behavior has not been fully studied so far. Here we report the preparation of a ZnO/Ag/Ag2WO4 photo-electrode with SPR behavior by a low temperature hydrothermal chemical growth method followed by a successive ionic layer adsorption and reaction (SILAR) method. The properties of the prepared samples were investigated by different characterization techniques, which confirm that Ag/Ag2WO4 was deposited on the ZnO NRs. The Ag2WO4/Ag/ZnO photo-electrode showed an enhancement in PEC performance compared to bare ZnO NRs. The observed enhancement is attributed to the red shift of the optical absorption spectrum of the Ag2WO4/Ag/ZnO to the visible region (>400 nm) and to the SPR effect of surface metallic silver (Ag0) particles from the Ag/Ag2WO4 that could generate electron-hole pairs under illumination of low energy visible sun light. Finally, we proposed the PEC mechanism of the Ag2WO4/Ag/ZnO photo-electrode with an energy band structure and possible electron-hole separation and transportation in the ZnO/Ag/Ag2WO4 heterostructure with SPR effect for water oxidation.

n-n ZnO-Ag2CrO4 heterojunction photoelectrodes with enhanced visible-light photoelectrochemical properties.

In this study, ZnO nanorods (NRs) were hydrothermally grown on an Au-coated glass substrate at a relatively low temperature (90 °C), followed by the deposition of Ag2CrO4 particles via a successive ionic layer adsorption and reaction (SILAR) route. The content of the Ag2CrO4 particles on ZnO NRs was controlled by changing the number of SILAR cycles. The fabricated ZnO-Ag2CrO4 heterojunction photoelectrodes were subjected to morphological, structural, compositional, and optical property analyses; their photoelectrochemical (PEC) properties were investigated under simulated solar light illumination. The photocurrent responses confirmed that the ability of the ZnO-Ag2CrO4 heterojunction photoelectrodes to separate the photo-generated electron-hole pairs is stronger than that of bare ZnO NRs. Impressively, the maximum photocurrent density of about 2.51 mA cm-2 at 1.23 V (vs. Ag/AgCl) was measured for the prepared ZnO-Ag2CrO4 photoelectrode with 8 SILAR cycles (denoted as ZnO-Ag2CrO4-8), which exhibited about 3-fold photo-enhancement in the current density as compared to bare ZnO NRs (0.87 mA cm-2) under similar conditions. The improvement in photoactivity was attributed to the ideal band gap and high absorption coefficient of the Ag2CrO4 particles, which resulted in improved solar light absorption properties. Furthermore, an appropriate annealing treatment was proven to be an efficient process to increase the crystallinity of Ag2CrO4 particles deposited on ZnO NRs, which improved the charge transport characteristics of the ZnO-Ag2CrO4-8 photoelectrode annealed at 200 °C and increased the performance of the photoelectrode. The results achieved in the present work present new insights for designing n-n heterojunction photoelectrodes for efficient and cost-effective PEC applications and solar-to-fuel energy conversions.

Graphene-based plasmonic nanocomposites for highly enhanced solar-driven photocatalytic activities.

High-efficiency photocatalysts are crucial for the removal of organic pollutants and environmental sustainability. In the present work, we report on a new low-temperature hydrothermal chemical method, assisted by ultrasonication, to synthesize disruptive plasmonic ZnO/graphene/Ag/AgI nanocomposites for solar-driven photocatalysis. The plasmonic nanocomposites were investigated by a wide range of characterization techniques, confirming successful formation of photocatalysts with excellent degradation efficiency. Using Congo red as a model dye molecule, our experimental results demonstrated a photocatalytic reactivity exceeding 90% efficiency after one hour simulated solar irradiation. The significantly enhanced degradation efficiency is attributed to improved electronic properties of the nanocomposites by hybridization of the graphene and to the addition of Ag/AgI which generates a strong surface plasmon resonance effect in the metallic silver further improving the photocatalytic activity and stability under solar irradiation. Scavenger experiments suggest that superoxide and hydroxyl radicals are responsible for the photodegradation of Congo red. Our findings are important for the fundamental understanding of the photocatalytic mechanism of ZnO/graphene/Ag/AgI nanocomposites and can lead to further development of novel efficient photocatalyst materials.

Efficient tri-metallic oxides NiCo2O4/CuO for the oxygen evolution reaction.

In this study, a simple approach was used to produce nonprecious, earth abundant, stable and environmentally friendly NiCo2O4/CuO composites for the oxygen evolution reaction (OER) in alkaline media. The nanocomposites were prepared by a low temperature aqueous chemical growth method. The morphology of the nanostructures was changed from nanowires to porous structures with the addition of CuO. The NiCo2O4/CuO composite was loaded onto a glassy carbon electrode by the drop casting method. The addition of CuO into NiCo2O4 led to reduction in the onset potential of the OER. Among the composites, 0.5 grams of CuO anchored with NiCo2O4 (sample 2) demonstrated a low onset potential of 1.46 V vs. a reversible hydrogen electrode (RHE). A current density of 10 mA cm-2 was achieved at an over-potential of 230 mV and sample 2 was found to be durable for 35 hours in alkaline media. Electrochemical impedance spectroscopy (EIS) indicated a small charge transfer resistance of 77.46 ohms for sample 2, which further strengthened the OER polarization curves and indicates the favorable OER kinetics. All of the obtained results could encourage the application of sample 2 in water splitting batteries and other energy related applications.

Nanoimmunosensor based on ZnO nanorods for ultrasensitive detection of 17ß-Estradiol.

Advances in nanostructured materials have facilitated the development of novel sensitive techniques for detection of environmental and clinical analytes. There is immense need for development of devices that can detect analytes at concentrations as low as few pg mL-1. The comparable size of nanostructured materials and biomolecules enabled the integration of biological systems with nanometer sized structures. Herein, we demonstrate a Zinc Oxide nanorods (ZnONRs) integrated ultrasensitive label-free biosensor with femtomolar (0.01 pg mL-1) sensitivity for the endocrine disruptor 17ß-Estradiol (E2). The ZnONRs, average width 50 nm and length 325 nm, were grown on the silver electrode surface (Ag-ZnONRs). Monoclonal antibodies of E2 (mAb-E2) were covalently immobilized on ZnONRs surface and measured using electrochemical impedance spectroscopy (EIS). A linear detection range of 0.1-200 pg mL-1 for E2 with R2 = 0.99 and % RSD = 4.35 (n = 3, assay volume 90 µL) was achieved for the developed nano-sensing system. A significant enhancement in the sensitivity was achieved in the presence of ZnONRs, enabling the limit of quantification down to 0.1 pg mL-1 with 2.7 % capacitance change per decade. In addition, a further increase in sensitivity due to assay volume reduction (20 µL) was observed enabling further scope of miniaturization.

Synthesis of Heart/Dumbbell-Like CuO Functional Nanostructures for the Development of Uric Acid Biosensor.

It is always demanded to prepare a nanostructured material with prominent functional properties for the development of a new generation of devices. This study is focused on the synthesis of heart/dumbbell-like CuO nanostructures using a low-temperature aqueous chemical growth method with vitamin B12 as a soft template and growth directing agent. CuO nanostructures are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) techniques. CuO nanostructures are heart/dumbbell like in shape, exhibit high crystalline quality as demonstrated by XRD, and have no impurity as confirmed by XPS. Apparently, CuO material seems to be porous in structure, which can easily carry large amount of enzyme molecules, thus enhanced performance is shown for the determination of uric acid. The working linear range of the biosensor is 0.001 mM to 10 mM with a detection limit of 0.0005 mM and a sensitivity of 61.88 mV/decade. The presented uric acid biosensor is highly stable, repeatable, and reproducible. The analytical practicality of the proposed uric acid biosensor is also monitored. The fabrication methodology is inexpensive, simple, and scalable, which ensures the capitalization of the developed uric acid biosensor for commercialization. Also, CuO material can be used for various applications such as solar cells, lithium ion batteries, and supercapacitors.