Polydopamine functionalized graphene sheets decorated with magnetic metal oxide nanoparticles as efficient nanozyme for the detection and degradation of harmful triazine pesticides.

A facile and an eco-friendly reduction and functionalization of reduced graphene oxide (rGO) sheets is carried out using dopamine and decorated with magnetic Fe3O4 nanoparticles with an average size of 12 nm by a simple co-precipitation method which is established as an artificial nanozyme. Here, functionalization of graphene using dopamine has introduced several advantages and insights into this study. The Fe3O4 nanoparticles decorated functionalized rGO sheets (FDGs) nanozymes are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric (TGA) and vibrating sample magnetometer (VSM) analysis. FDGs nanozymes exhibits dual characteristics towards detection and degradation of harmful simazine pesticide. The hydrogen bonding interactions between pesticide molecules and 3,3',5,5'-tetramethylbenzidine (TMB) causes inhibition of the catalytic activity of the FDGs towards oxidation of TMB molecule. Based on that, the presence of simazine pesticide in an aqueous medium can be easily determined and a certain value (2.24 µM) of detection limit was achieved. The photocatalytic degradation of simazine is also executed and excellent photocatalytic activity was observed under irradiation of direct natural sunlight. The FDGs nanozyme is also reusable up to several times with insignificant loss in its catalytic activity towards simazine degradation.

Biocompatible functionalized AuPd bimetallic nanoparticles decorated on reduced graphene oxide sheets for photothermal therapy of targeted cancer cells.

Graphene, which is a unique 2D nanomaterials has received widespread attention for photothermal therapy (PTT) application. Here, we have designed the nanocomposite using polydopamine (PDA) functionalized reduced graphene oxide (rGO) nanosheets and bimetallic AuPd nanoparticles (NPs). The bimetallic AuPd nanoparticles decorated PDA functionalized rGO (AuPd-rGO/PDA) nanocomposite is synthesized by simple chemical reduction technique resulting in an average size of AuPd bimetallic nanostructure of 4.18 nm. The photothermal activity of the AuPd-rGO/PDA nanocomposite is explored under the irradiation of near infrared (NIR) laser sources of wavelength 915 nm. The temperature rises nearly 51 ± 3 °C within 3 min of irradiation NIR laser light resulting in the ablation of MDAMB-231 cancer cells up to concentration of 25 µg mL-1 of AuPd-rGO/PDA nanocomposite. This high performance of the ablation of cancer cells by photothermal therapy technique was facilitated using a low concentration of the nanocomposite by the synergistic effects of the bimetallic AuPd as well as rGO and PDA functionalization. The AuPd-rGO/PDA nanocomposite demonstrated the high biocompatibility towards normal healthy cell lines (L929) and exhibits survival efficiency of more than 85%. We also demonstrated the biocompatibility of the AuPd-rGO/PDA nanocomposite materials on the zebrafish embryos (Danio rerio). This work thus illustrates that the AuPd-rGO/PDA nanocomposite could behave as favourable nanoplatform for tumor therapeutics.

Ag and Au nanoparticles/reduced graphene oxide composite materials: Synthesis and application in diagnostics and therapeutics.

The exceptional electrical, thermal, optical and mechanical properties have made two dimensional sp2 hybridized graphene a material of choice in both academic as well as industrial research. In the last few years, researchers have devoted their efforts towards the development of graphene/polymer, graphene/metal nanoparticle and graphene/ceramic nanocomposites. These materials display excellent mechanical, electrical, thermal, catalytic, magnetic and optical properties which cannot be obtained separately from the individual components. Fascinating physical and chemical properties are displayed by noble metal nanomaterials and thus they represent model building blocks for modifying nanoscale structures for diverse applications extending from catalysis, optics to nanomedicine. Insertion of noble metal (Au, Ag) nanoparticles (NPs) into chemically derived graphene is thus of primary importance to open new avenues for both materials in various fields where the specific properties of each material act synergistically to provide hybrid materials with exceptional performances. This review attempts to summarize the different synthetic procedures for the preparation of Ag and Au NPs/reduced graphene oxide (rGO) composites. The synthesis processes of metal NPs/rGO composites are categorised into in-situ and ex-situ techniques. The in-situ approach consists of simultaneous reduction of metal salts and GO to obtain metal NPs/rGO nanocomposite materials, while in the ex-situ process, the metal NPs of desired size and shape are first synthesized and then transferred onto the GO or rGO matrix. The application of the Ag NPs and Au NPs/rGO composite materials in the area of biomedical (drug delivery and photothermal therapy) and biosensing are the focus of this review article.

Pt-Decorated Boron Nitride Nanosheets as Artificial Nanozyme for Detection of Dopamine.

Over the past decade, nanosized metal oxides, metals, and bimetallic particles have been actively researched as enzyme mimetic nanomaterials. However, the common issues with individual nanoparticles (NPs) are stabilization, reproducibility, and blocking of active sites by surfactants. These problems promote further studies of composite materials, where NPs are spread on supports, such as graphene derivatives or dichalcogenide nanosheets. Another promising type of support for NPs is the few-layered hexagonal boron nitride (hBN). In this study, we develop surfactant-free nanocomposites containing Pt NPs dispersed on chemically modified hydrophilic hBN nanosheets (hBNNSs). Ascorbic acid was used as a reducing agent for the chemical reduction of the Pt salt in the presence of hBNNS aqueous colloid, resulting in Pt/hBNNS nanocomposites, which were thoroughly characterized with X-ray diffraction, transmission electron microscopy, dynamic light scattering, and X-ray photoelectron and infrared spectroscopies. Similar to graphene oxide binding the metal NPs more efficiently than pure graphene, hydrophilic hBNNSs well stabilize Pt NPs, with particle size down to around 8 nm. We further demonstrate for the first time that Pt/hBNNS nanocomposites exhibit peroxidase-like catalytic activity, accelerating the oxidation of the classical colorless peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) to its corresponding blue-colored oxidized product in the presence of H2O2. Kinetic and mechanism studies involving terephthalic acid and isopropanol as a fluorescent probe and an •OH radical scavenger, respectively, proved that Pt/hBNNSs assist H2O2 decomposition to active oxygen species (•OH), which are responsible for TMB oxidation. The Pt/hBNNS nanocomposite-assisted oxidation of TMB provides an effective platform for the colorimetric detection of dopamine, an important biomolecule. The presence of increased amounts of dopamine gradually inhibits the catalytic activity of Pt/hBNNSs for the oxidation of TMB by H2O2, thus enabling selective sensing of dopamine down to 0.76 µM, even in the presence of common interfering molecules and on real blood serum samples. The present investigation on Pt/hBNNSs contributes to the knowledge of hBN-based nanocomposites and discovers their new usage as nanomaterials with good enzyme-mimicking activity and dopamine-sensing properties.

Dual responsive magnetic Au@Ni nanostructures loaded reduced graphene oxide sheets for colorimetric detection and photocatalytic degradation of toxic phenolic compounds.

We report the colorimetric detection and photocatalytic degradation of toxic phenolic compounds using Au@Ni loaded reduced graphene oxide (rGO) nanostructures. Core-shell nanoparticles of Au and Ni are successfully designed on rGO with size <8 nm by a solvothermal route which demonstrate excellent enzyme mimic behaviour towards the oxidation of 3,3',5,5' tetramethylbenzidine (TMB), a peroxidase substrate and towards colorimetric detection of phenols with detection limit as low as 1.68 µM, wide detection range of 1-300 µM and admirable selectivity. Additionally, the Au@Ni/rGO nanocomposite exhibits excellent photo responsive behaviour towards degradation of phenol, 2-chlorophenol (2-CP) and 2-nitrophenol (2-NP) under natural sunlight irradiation with more than 87% degradation. The superiority of the bimetallic nanocomposite is established by comparing its activity to its monometallic counterparts. The sustainability of the nanocomposite is assessed through the reusability in the photocatalytic reaction upto six consecutive cycles without significant loss in activity. This is the first study where nanomaterials are used for both detection and degradation of environmental pollutants with positive and encouraging results.

Colorimetric determination of glucose in solution and via the use of a paper strip by exploiting the peroxidase and oxidase mimicking activity of bimetallic Cu-Pd nanoparticles deposited on reduced graphene oxide, graphitic carbon nitride, or MoS2 nanosheets.

This work describes the preparation of bimetallic Cu-Pd nanoparticles (NPs) on supports like reduced graphene oxide (rGO), graphitic carbon nitride (g-C3N4) and MoS2 sheets with a size of <10 nm. rGO is found to be the best support for synthesizing Cu-Pd NPs with controlled shape, size and oxidation state. The Cu-Pd/rGO nanocomposite also demonstrated the best peroxidase and oxidase mimicking activity compared to Cu-Pd/g-C3N4 and Cu-Pd/MoS2 nanocomposites. The peroxidase mimicking activity of Cu-Pd/rGO was investigated in more detail, and a glucose oxidase (GOx) based glucose sensor was constructed that is based on the enzymatic formation of H2O2 and the Cu-Pd NPs-assisted oxidation of tetramethylbenzidine by H2O2 to give a blue-green coloration with absorption maxima at 652 nm. The assay has a 0.29 µM detection limit and a detection range that extends from 0.2 to 50 µM. The method was applied to the determination of glucose in diluted serum samples, and results compared well to those acquired with a clinical analyzer. The method also was applied in a colorimetric paper-based test stripe that can detect glucose within 10 min. Graphical abstract Schematic representation of a sensitive colorimetric glucose assay based on bimetallic Cu-Pd nanoparticles supported on 2D nanosheets, and construction of a paper based device for rapid glucose detection.

Bimetallic Au-Pd nanoparticles on 2D supported graphitic carbon nitride and reduced graphene oxide sheets: A comparative photocatalytic degradation study of organic pollutants in water.

Novel and sustainable bimetallic nanoparticles of Au-Pd on 2D graphitic carbon nitride (g-C3N4) and reduced graphene oxide (rGO) sheets was designed adopting an eco-friendly chemical route to obtain Au-Pd/g-C3N4 and Au-Pd/rGO, respectively. Elimination of hazardous pollutants, particularly phenol from water is urgent for environment remediation due to its significant carcinogenicity. Considering this aspect, the Au-Pd/g-C3N4 and Au-Pd/rGO nanocomposites are used as photocatalyst towards degradation of toxic phenol, 2-chlorophenol (2-CP) and 2-nitrophenol (2-NP) under natural sunlight and UV light irradiation. Au-Pd/g-C3N4 nanocomposite exhibited higher activity then Au/g-C3N4, Pd/g-C3N4 and Au-Pd/rGO nanocomposites with more than 95% degradation in 180 min under sunlight. The obtained degradation efficiency of our materials is better than many other reported photocatalysts. Incorporation of nitrogen atoms in the carbon skeleton of g-C3N4 provides much better properties to Au-Pd/g-C3N4 nanocomposite than carbon based Au-Pd/rGO leading to its higher degradation efficiency. Due to the presence of these nitrogen atoms and some defects, g-C3N4 possesses appealing electrical, chemical and functional properties. Photoluminescence results further revealed the efficient charge separation and delayed recombination of photo-induced electron-hole pairs in the Au-Pd/g-C3N4 nanocomposite. Generation of reactive oxygen species during photocatalysis is well explained through photoluminescence study and the sustainability of these photocatalyst was ascertained through reusability study up to eight and five consecutive cycles for Au-Pd/g-C3N4 and Au-Pd/rGO nanocomposites, respectively without substantial loss in its activity. Characterization of the photocatalysts after reaction signified the stability of the nanocomposites and added advantage to our developed photocatalytic system.

Correction: Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water.

Correction for 'Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water' by Gitashree Darabdhara, et al., Nanoscale, 2016, 8, 8276-8287.

Aluminum Titania Nanoparticle Composites as Nonprecious Catalysts for Efficient Electrochemical Generation of H2.

In this paper, we demonstrated, for the first time, aluminum titania nanoparticle (Al-TiO2 NP) composites with variable amounts of TiO2 NPs as nonprecious active catalysts for the electrochemical generation of H2. These materials were synthesized by mixing desired amounts of hydrogen titanate nanotubes (TNTs), fabricated here by a cost-effective approach at moderate hydrothermal conditions, with aluminum powder (purity 99.7%; size 35 µm). The mixture was compacted under an applied uniaxial stress of 300 MPa followed by sintering at 500 °C for 1 h. After sintering had been completed, all TNTs were found to convert to TiO2 NPs (average particle size 15 nm). Finally, Al-xTiO2 NP nanocomposites (x = 1, 3, 5, and 10) were obtained and characterized by scanning electron microscopy/energy-dispersive X-ray, X-ray diffraction, and X-ray photoelectron spectroscopy. The hydrogen evolution reaction (HER) activity of these materials was studied in 0.5 M H2SO4 at 298 K using polarization and impedance measurements. The nanocomposite of chemical composition Al-5% TiO2 NPs showed the best catalytic performance for the HER, with an onset potential (EHER), a Tafel slope (ßc), and an exchange current density (j0) of -100 mV (RHE), 59.8 mV decade(-1), and 0.14 mA cm(-2), respectively. This HER activity is not far from that of the commercial platinum/carbon catalyst (EHER = 0.0 mV, ßc = 31 mV dec(-1), and j0 = 0.78 mA cm(-2)). The best catalyst also exhibited good stability after 10000 repetitive cycles with negligible loss in current.

Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water.

Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles are successfully prepared via a chemical approach consisting of reducing the metal precursors using ascorbic acid as reductant at an elevated temperature. The prepared nanocomposite is employed as a photocatalyst for the degradation of organic contaminants such as phenol, 2-chlorophenol (2-CP), and 2-nitrophenol (2-NP). The complete degradation of phenol is achieved after 300 min under natural sunlight irradiation whereas the degradation of 2-CP and 2-NP is completed after 180 min. The activity of the photocatalyst is evaluated considering several parameters such as the initial phenol concentration, the photocatalyst loading, and the pH of the solution. The degradation kinetics of all the compounds is carefully studied and found to follow a linear Langmuir-Hinshelwood model. Furthermore, the reusability of the photocatalyst is successfully achieved up to five cycles and the catalyst exhibits an excellent stability.

Reduced graphene oxide nanosheets decorated with AuPd bimetallic nanoparticles: a multifunctional material for photothermal therapy of cancer cells.

Gold nanoparticles (Au NPs) and reduced graphene oxide (rGO) mediated hyperthermia are the two most widely explored systems used for the photothermal ablation of cancer cells. We show that the photothermal conversion and efficiency of these nanomaterials can be improved not only by combining them into one material, but also by forming bimetallic AuPd embedded on rGO. The AuPd NPs-rGO nanocomposites were prepared by a simple one-step chemical reduction technique using the individual metallic salts, graphene oxide (GO) and ascorbic acid as a green reducing agent. The AuPd NPs-rGO nanocomposites were covalently functionalized with poly(ethylene glycol) (PEG) chains and characterized by high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and UV/Vis spectrophotometry. Covalent attachment of PEG units to the AuPd NPs-rGO nanocomposites greatly improved the solubility and stability of the nanocomposites in biological media and ensured its biocompatibility towards cancer cells such as HeLa cells. The near-infrared photothermal properties of AuPd NPs-rGO-PEG nanocomposites were evaluated using a continuous laser at 800 nm with power densities between 0.5 and 2 W cm-2. The nanocomposite was successfully used for the in vitro photothermal ablation of HeLa cells. At 1 W cm-2, the total killing of HeLa cells was achieved through irradiation of AuPd NPs-rGO-PEG nanocomposites incubated cells for 10 min at a particle concentration of 20 µg mL-1. Such high efficiency was principally assigned to the synergetic effects of rGO and AuPd NPs.