Biofunctionalized CdS Quantum Dots: A Case Study on Nanomaterial Toxicity in the Photocatalytic Wastewater Treatment Process.

The toxic nature of inorganic nanostructured materials as photocatalysts is often not accounted for in traditional wastewater treatment reactions. Particularly, some inorganic nanomaterials employed as photocatalysts may release secondary pollutants in the form of ionic species that leach out due to photocorrosion. In this context, this work is a proof-of-concept study for exploring the environmental toxicity effect of extremely small-sized nanoparticles (<10 nm) like quantum dots (QDs) that are employed as photocatalysts, and in this study, cadmium sulfide (CdS) QDs are chosen. Typically, CdS is an excellent semiconductor with suitable bandgap and band-edge positions that is attractive for applications in solar cells, photocatalysis, and bioimaging. However, the leaching of toxic cadmium (Cd2+) metal ions due to the poor photocorrosion stability of CdS is a matter of serious concern. Therefore, in this report, a cost-effective strategy is devised for biofunctionalizing the active surface of CdS QDs by employing tea leaf extract, which is expected to hinder photocorrosion and prevent the leaching of toxic Cd2+ ions. The coating of tea leaf moieties (chlorophyll and polyphenol) over the CdS QDs (referred to hereafter as G-CdS QDs) was confirmed through structural, morphological, and chemical analysis. Moreover, the enhanced visible-light absorption and emission intensity of G-CdS QDs in comparison to that of C-CdS QDs synthesized through a conventional chemical synthesis approach confirmed the presence of chlorophyll/polyphenol coating. Interestingly, the polyphenol/chlorophyll molecules formed a heterojunction with CdS QDs and enabled the G-CdS QDs to exhibit enhanced photocatalytic activity in the degradation of methylene blue dye molecules over C-CdS QDs while effectively preventing photocorrosion as confirmed from cyclic photodegradation studies. Furthermore, detailed toxicity studies were conducted by exposing zebrafish embryos to the as-synthesized CdS QDs for 72 h. Surprisingly, the survival rate of the zebrafish embryos exposed to G-CdS QDs was equal to that of the control, indicating a significant reduction in the leaching of Cd2+ ions from G-CdS QDs in comparison to C-CdS QDs. The chemical environment of C-CdS and G-CdS before and after the photocatalysis reaction was examined by X-ray photoelectron spectroscopy. These experimental findings prove that biocompatibility and toxicity could be controlled by simply adding tea leaf extract during the synthesis of nanostructured materials, and revisiting green synthesis techniques can be beneficial. Furthermore, repurposing the discarded tea leaves may not only facilitate the control of toxicity of inorganic nanostructured materials but can also help in enhancing global environmental sustainability.

Assessing Surface Coverage of Aminophenyl Bonding Sites on Diazotised Glassy Carbon Electrodes for Optimised Electrochemical Biosensor Performance.

Electrochemical biosensors using carbon-based electrodes are being widely developed for the detection of a range of different diseases. Since their sensitivity depends on the surface coverage of bioreceptor moieties, it necessarily depends on the surface coverage of amine precursors. Electrochemical techniques, using ferrocene carboxylic acid as a rapid and cheap assay, were used to assess the surface coverage of amino-phenyl groups attached to the carbon electrode. While the number of electrons transferred in the first step of diazotisation indicated a surface coverage of 8.02 ± 0.2 × l0-10 (mol/cm2), and those transferred in the second step, a reduction of nitrophenyl to amino-phenyl, indicated an amine surface coverage of 4-5 × l0-10 (mol/cm2), the number of electrons transferred during attachment of the amine coupling assay compound, ferrocene carboxylic acid, indicated a much lower available amine coverage of only 2.2 × l0-11 (mol/cm2). Furthermore, the available amine coverage was critically dependent upon the number of cyclic voltammetry cycles used in the reduction, and thus the procedures used in this step influenced the sensitivity of any subsequent sensor. Amine coupling of a carboxyl terminated anti-beta amyloid antibody specific to Aß(1-42) peptide, a potential marker for Alzheimer's disease, followed the same pattern of coverage as that observed with ferrocene carboxylic acid, and at optimum amine coverage, the sensitivity of the differential pulse voltammetry sensor was in the range 0-200 ng/mL with the slope of 5.07 µA/ng.mL-1 and R2 = 0.98.

Graphene based electrochemical immunosensor for the ultra-sensitive label free detection of Alzheimer's beta amyloid peptides Aß(1-42).

An immunosensor capable of high sensitivity detection of beta-amyloid peptides, shown to be a reliable biomarker for Alzheimer's disease, has been developed using screen printed graphene electrodes (SPGEs) modified with ultra-thin layers of polymerised 1,5-diaminonaphthalene (pDAN). Electropolymerization of 1,5-diaminonaphthalene (DAN) was performed to coat the graphene screen printed electrodes in a continuous polymer layer with controlled thickness. The surface characteristics of pristine graphene and polymer modified graphene electrodes were examined using Raman and X-ray photoelectron spectroscopy. The effects of polymer thickness on the electron transfer rates were investigated. An immunosensor for selective detection of beta amyloid peptides Aß(1-42) was developed via biofunctionalization of the pDAN modified SPGE with the anti-beta amyloid antibody used as the peptide bioreceptor. The immunosensor has been used for specific detection of Aß(1-42) with a linear range of 1 pg mL-1 to 1000 pg mL-1 and showed 1.4 pg mL-1 and 4.25 pg mL-1 detection and quantification limit, respectively. The biosensor was further validated for the analysis of spiked human plasma. The immunosensor enables rapid, accurate, precise, reproducible and highly sensitive detection of Aß(1-42) using a low-cost SPGE platform, which opens the possibilities for diagnostic ex vivo applications and research-based real time studies.

A Facile Method for the Non-Covalent Amine Functionalization of Carbon-Based Surfaces for Use in Biosensor Development.

Affinity biosensors based on graphene field-effect transistor (GFET) or resistor designs require the utilization of graphene's exceptional electrical properties. Therefore, it is critical when designing these sensors, that the electrical properties of graphene are maintained throughout the functionalization process. To that end, non-covalent functionalization may be preferred over covalent modification. Drop-cast 1,5-diaminonaphthalene (DAN) was investigated as a quick and simple method for the non-covalent amine functionalization of carbon-based surfaces such as graphene, for use in biosensor development. In this work, multiple graphene surfaces were functionalized with DAN via a drop-cast method, leading to amine moieties, available for subsequent attachment to receptor molecules. Successful modification of graphene with DAN via a drop-cast method was confirmed using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and real-time resistance measurements. Successful attachment of receptor molecules also confirmed using the aforementioned techniques. Furthermore, an investigation into the effect of sequential wash steps which are required in biosensor manufacture, on the presence of the DAN layer, confirmed that the functional layer was not removed, even after multiple solvent exposures. Drop-cast DAN is thus, a viable fast and robust method for the amine functionalization of graphene surfaces for use in biosensor development.

Ultrathin Functional Polymer Modified Graphene for Enhanced Enzymatic Electrochemical Sensing.

Grafting thin polymer layers on graphene enables coupling target biomolecules to graphene surfaces, especially through amide and aldehyde linkages with carboxylic acid and primary amine derivatives, respectively. However, functionalizing monolayer graphene with thin polymer layers without affecting their exceptional electrical properties remains challenging. Herein, we demonstrate the controlled modification of chemical vapor deposition (CVD) grown single layer graphene with ultrathin polymer 1,5-diaminonaphthalene (DAN) layers using the electropolymerization technique. It is observed that the controlled electropolymerization of DAN monomer offers continuous polymer layers with thickness ranging between 5⁻25 nm. The surface characteristics of pure and polymer modified graphene was examined. As anticipated, the number of surface amine groups increases with increases in the layer thickness. The effects of polymer thickness on the electron transfer rates were studied in detail and a simple route for the estimation of surface coverage of amine groups was demonstrated using the electrochemical analysis. The implications of grafting ultrathin polymer layers on graphene towards horseradish peroxidase (HRP) enzyme immobilization and enzymatic electrochemical sensing of H2O2 were discussed elaborately.

Graphene Field Effect Transistors for Biomedical Applications: Current Status and Future Prospects.

Since the discovery of the two-dimensional (2D) carbon material, graphene, just over a decade ago, the development of graphene-based field effect transistors (G-FETs) has become a widely researched area, particularly for use in point-of-care biomedical applications. G-FETs are particularly attractive as next generation bioelectronics due to their mass-scalability and low cost of the technology's manufacture. Furthermore, G-FETs offer the potential to complete label-free, rapid, and highly sensitive analysis coupled with a high sample throughput. These properties, coupled with the potential for integration into portable instrumentation, contribute to G-FETs' suitability for point-of-care diagnostics. This review focuses on elucidating the recent developments in the field of G-FET sensors that act on a bioaffinity basis, whereby a binding event between a bioreceptor and the target analyte is transduced into an electrical signal at the G-FET surface. Recognizing and quantifying these target analytes accurately and reliably is essential in diagnosing many diseases, therefore it is vital to design the G-FET with care. Taking into account some limitations of the sensor platform, such as Debye-Hükel screening and device surface area, is fundamental in developing improved bioelectronics for applications in the clinical setting. This review highlights some efforts undertaken in facing these limitations in order to bring G-FET development for biomedical applications forward.

The Application of Graphene and Its Derivatives to Energy Conversion, Storage, and Environmental and Biosensing Devices.

Graphene (GR) and its derivatives are promising materials on the horizon of nanotechnology and material science and have attracted a tremendous amount of research interest in recent years. The unique atom-thick 2D structure with sp(2) hybridization and large specific surface area, high thermal conductivity, superior electron mobility, and chemical stability have made GR and its derivatives extremely attractive components for composite materials for solar energy conversion, energy storage, environmental purification, and biosensor applications. This review gives a brief introduction of GR's unique structure, band structure engineering, physical and chemical properties, and recent energy-related progress of GR-based materials in the fields of energy conversion (e.g., photocatalysis, photoelectrochemical water splitting, CO2 reduction, dye-sensitized and organic solar cells, and photosensitizers in photovoltaic devices) and energy storage (batteries, fuel cells, and supercapacitors). The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing, and removal of heavy-metal ions is presented. Additionally, the use of graphene composites in the biosensing field is discussed. We conclude the review with remarks on the challenges, prospects, and further development of GR-based materials in the exciting fields of energy, environment, and bioscience.

Single-step electrospun TiO2-Au hybrid electrodes for high selectivity photoelectrocatalytic glutathione bioanalysis.

Understanding the fundamentals of photoelectrocatalytic (PEC) biomolecular oxidation benefits the development of next-generation PEC biosensors. In this work, single-step electrospun titanium-di-oxide-gold (TiO2-Au) hybrid nanofibers (HNF) are reported as being a potential candidate for PEC glutathione (GSH) bioanalysis. The chemical environment of TiO2 and TiO2-Au HNFs were studied with X-ray photoelectron spectroscopy and found to have a strong electronic interaction between TiO2 and the Au nanoparticles (NPs). The PEC measurements revealed that the intramolecular backbone hydrogen bonding of GSH molecules predominantly contributes highly active Au-GSH bio-nano interfaces, which facilitate the PEC oxidation rate of GSH and thus enhance the photocurrent. Furthermore, the Au NPs present act as auxiliary electron transport channels resulting in enhanced charge collection at the external circuit. As a result, the TiO2-Au electrode generated a two-fold higher photocurrent density of ∼84.4 µA cm-2 in the presence of 0.5 mM GSH, where the pristine TiO2 NFs displayed only a negligible influence. Likewise, the TiO2-Au HNF electrode showed a higher sensitivity of 0.002 mM and a wide linear detection range between 0.022 mM and 0.7 mM, with a superior selectivity towards GSH bioanalysis over ascorbic acid and glucose at -0.33 V (versus silver/silver chloride) than that obtained with pristine TiO2. The implications of these findings towards the development of a next-generation PEC biosensor are discussed.

Modulating the interaction between gold and TiO2 nanowires for enhanced solar driven photoelectrocatalytic hydrogen generation.

The interaction strength of Au nanoparticles with pristine and nitrogen doped TiO2 nanowire surfaces was analysed using density functional theory and their significance in enhancing the solar driven photoelectrocatalytic properties was elucidated. In this article, we prepared 4-dimethylaminopyridine capped Au nanoparticle decorated TiO2 nanowire systems. The density functional theory calculations show {101} facets of TiO2 as the preferred phase for dimethylaminopyridine-Au nanoparticles anchoring with a binding energy of -8.282 kcal mol(-1). Besides, the interaction strength of Au nanoparticles was enhanced nearly four-fold (-35.559 kcal mol(-1)) at {101} facets via nitrogen doping, which indeed amplified the Au nanoparticle density on nitrided TiO2. The Au coated nitrogen doped TiO2 (N-TiO2-Au) hybrid electrodes show higher absorbance owing to the light scattering effect of Au nanoparticles. In addition, N-TiO2-Au hybrid electrodes block the charge leakage from the electrode to the electrolyte and thus reduce the charge recombination at the electrode/electrolyte interface. Despite the beneficial band narrowing effect of nitrogen in TiO2 on the electrochemical and visible light activity in N-TiO2-Au hybrid electrodes, it results in low photocurrent generation at higher Au NP loading (3.4 × 10(-7) M) due to light blocking the N-TiO2 surface. Strikingly, even with a ten-fold lower Au NP loading (0.34 × 10(-7) M), the synergistic effects of nitrogen doping and Au NPs on the N-TiO2-Au hybrid system yield high photocurrent compared to TiO2 and TiO2-Au electrodes. As a result, the N-TiO2-Au electrode produces nearly 270 µmol h(-1) cm(-2) hydrogen, which is nearly two-fold higher than the pristine TiO2 counterpart. The implications of these findings for the design of efficient hybrid photoelectrocatalytic electrodes are discussed.

Pt-free solar driven photoelectrochemical hydrogen fuel generation using 1T MoS2 co-catalyst assembled CdS QDs/TiO2 photoelectrode.

The solar-to-hydrogen generation from the TiO2-CdS-ZnS-MoS2 (TCZM) heterointerface was demonstrated. We found that a Pt-free CdS quantum dot-sensitized TiO2 mesoporous electrode with a metallic-type 1T MoS2 co-catalyst resulted in 0.11 ml cm(-2) h(-1) H2 fuel generation in unassisted potential mode, which was strikingly improved to 1.47 ml cm(-2) h(-1) under 1 V applied potential.

Simultaneous glucose sensing and biohydrogen evolution from direct photoelectrocatalytic glucose oxidation on robust Cu2O-TiO2 electrodes.

We report simultaneous photoelectrocatalytic (PEC) glucose sensing and biohydrogen generation for the first time from the direct PEC oxidation of glucose at multifunctional and robust Cu2O-TiO2 photocatalysts. Striking improvement of 30% in overall H2 gas evolution (∼122 µmol h(-1) cm(-2)) by photoholes assisted glucose oxidation opens a new platform in solar-driven PEC biohydrogen generation.

Enhanced photocatalytic performance at a Au/N-TiO2 hollow nanowire array by a combination of light scattering and reduced recombination.

We demonstrate one-step gold nanoparticle (AuNP) coating and the surface nitridation of TiO2 nanowires (TiO2-NWs) to amplify visible-light photon reflection. The surface nitridation of TiO2-NW arrays maximizes the anchoring of AuNPs, and the subsequent reduction of the band gap energy from 3.26 eV to 2.69 eV affords visible-light activity. The finite-difference time-domain (FDTD) simulation method clearly exhibits the enhancement in the strengths of localized electric fields between AuNPs and the nanowires, which significantly improves the photocatalytic (PC) performance. Both nitridation and AuNP decoration of TiO2-NWs result in beneficial effects of high (e(-)/h(+)) pair separation through healing of the oxygen vacancies. The combined effect of harvesting visible-light photons and reducing recombination in Au/N-doped TiO2-NWs promotes the photocatalytic activity towards degradation of methyl orange to an unprecedented level, ∼4 fold (1.1 × 10(-2) min) more than does TiO2-NWs (2.9 × 10(-3) min(-1)). The proposed AuNP decoration of nitridated TiO2-NW surfaces can be applied to a wide range of n-type metal oxides for photoanodes in photocatalytic applications.

Synergistic metal-metal oxide nanoparticles supported electrocatalytic graphene for improved photoelectrochemical glucose oxidation.

We report the fabrication of graphene-WO3-Au hybrid membranes and evaluate their photocatalytic activity towards glucose oxidase mediated enzymatic glucose oxidation. The dual-functionality of gold nanoparticles in the reinforcement of visible light activity of graphene-WO3 membranes and improving the catalytic activity of immobilized enzymes for unique photoelectrochemical sensing application is demonstrated. This work provides new insights into the fabrication of light-sensitive hybrid materials and facilitates their application in future.

Gold nanoparticle-composite nanofibers for enzymatic electrochemical sensing of hydrogen peroxide.

Robust composite nanofibers (NFs) are prerequisite for highly efficient electrochemical sensors. We report the electrochemical application of gold nanoparticle (Au NP)-composite Nafion NFs using a facile electrospinning technique. Owing to the uniform distribution and large surface area of the Au NPs in the NFs, the Au NP-composite electrodes gave rise to greatly improved electrochemical properties, compared to AuNP-free composite electrodes. When they were employed as reservoirs for immobilizing horseradish peroxidase (HRP), reliable and sensitive electrochemical detection by the enzyme reaction was achieved. The detection sensitivity for H2O2 was determined to be as low as 38 nM, which was one order higher than that of previous electrochemical sensors. In addition, there was no change in the enzyme stability over three weeks. In this regard, the developed NP/NF-based electrochemical sensors are anticipated to be very suitable for monitoring other enzyme reactions with high sensitivity and stability.

Dominant factors governing the rate capability of a TiO2 nanotube anode for high power lithium ion batteries.

Titanium dioxide (TiO(2)) is one of the most promising anode materials for lithium ion batteries due to low cost and structural stability during Li insertion/extraction. However, its poor rate capability limits its practical use. Although various approaches have been explored to overcome this problem, previous reports have mainly focused on the enhancement of both the electronic conductivity and the kinetic associated with lithium in the composite film of active material/conducting agent/binder. Here, we systematically explore the effect of the contact resistance between a current collector and a composite film of active material/conducting agent/binder on the rate capability of a TiO(2)-based electrode. The vertically aligned TiO(2) nanotubes arrays, directly grown on the current collector, with sealed cap and unsealed cap, and conventional randomly oriented TiO(2) nanotubes electrodes were prepared for this study. The vertically aligned TiO(2) nanotubes array electrode with unsealed cap showed superior performance with six times higher capacity at 10 C rate compared to conventional randomly oriented TiO(2) nanotubes electrode with 10 wt % conducting agent. On the basis of the detailed experimental results and associated theoretical analysis, we demonstrate that the reduction of the contact resistance between electrode and current collector plays an important role in improving the electronic conductivity of the overall electrode system.

Electrochemiluminescent metallopolymer-nanoparticle composites: nanoparticle size effects.

Metallopolymer-gold nanocomposites have been synthesized in which the metal complex-Au nanoparticle (NP) mole ratio is systematically varied by mixing solutions of 4-(dimethylamino) pyridine protected gold nanoparticles and a [Ru(bpy)(2)PVP(10)](2+) metallopolymer; bpy is 2,2'-bipyridyl and PVP is poly-(4-vinylpyridine). The impact of changing the gold nanoparticle diameter ranging from 4.0 ± 0.5 to 12.5 ± 1 nm has been investigated. The photo induced emission of the metallopolymer undergoes static quenching by the metal nanoparticles irrespective of their size. When the volume ratio of Au NP-Ru is 1, the quenching efficiency increases from 38% to 93% on going from 4.0 ± 0.5 to 12.5 ± 1 nm diameter nanoparticles while the radius of the quenching sphere remains unaffected at 75 ± 5 Å. The conductivity of thin films is initially unaffected by nanoparticle incorporation until a percolation threshold is reached at a mole ratio of 4.95 × 10(-2) after which the conductivity increases before reaching a maximum. For thin films of the nanocomposites on electrodes, the electrochemiluminescence intensity of the nanocomposite initially increases as nanoparticles are added before decreasing for the highest loadings. The electrochemiluminescence intensity increases with increasing nanoparticle diameter. The electrochemiluminescence (ECL) emission intensity of the nanocomposite formed using 12.5 nm particles at mole ratios between 5 × 10(-3) and 10 × 10(-3) is approximately 7-fold higher than that found for the parent metallopolymer. The application of these materials for low cost ECL-based point of care devices is discussed.

Enhanced electrochemiluminescence and charge transport through films of metallopolymer-gold nanoparticle composites.

Water-soluble 4-(dimethylamino) pyridine (DMAP) stabilized gold nanoparticles (DMAP-AuNP) were synthesized by ligand exchange and phase transfer (toluene/water). The DMAP-AuNPs are positively charged with the core diameter of 4 +/- 1 nm. Metallopolymer-gold nanocomposites were prepared by mixing gold nanoparticles and [Ru(bpy)(2)PVP(10)](ClO(4))(2), in water at different mole ratios; bpy is 2,2'-bipyridyl and PVP is poly (4-vinylpyridine). The photoluminescence emission intensity of the metallopolymer decreases with increasing AuNP loading and approximately 57% of the emission intensity is quenched when the Au NP:Ru mole ratio is 14.8 x 10(-2). The rate of homogeneous charge transfer through thin layers of the nanocomposite deposited on glassy carbon electrodes increases with increasing nanoparticle loading. The homogeneous charge transport diffusion coefficient, D(CT), for the composite (AuNP:Ru mole ratio 13.2 x 10(-2)) is (2.8 +/- 0.8) x 10(-11) cm(2) s(-1) and is approximately 3-fold higher than that found for the pure metallopolymer. Significantly, despite the ability of the metal nanoparticles to quench the ruthenium-based emission, the electrochemiluminescence of the nanocomposite with a AuNP:Ru mole ratio of 4.95 x 10(-2) is approximately three times more intense than the parent metallopolymer. This enhancement arises from the increased rate of charge transport that leads to a greater number of excited states per unit time while minimizing the quenching effects. The implications of these findings for the design of electrochemiluminescent sensors are discussed.