Thin PEGylated Carbon Nitrides: Water-Dispersible Organic Nanodots as Bioimaging Probes.

Fluorescent materials are being used for the optical/fluorescence imaging of living cells and animal models. As such, the development of heavy-metal-free, water-dispersible, and biocompatible imaging probes is still important. Carbon nitride (C3 N4 ) is used as a bioimaging probe due to its suitable optical properties, thus enhancing its biocompatibility and dispersibility in aqueous media is required. In this study, we incorporated short-chain polyethylene glycol (PEG) groups onto a carbon nitride network by the simple N-alkylation of hexaethylene glycolic mesylate with nucleophilic nitrogen atoms on oxidized carbon nitride (OCN). The PEGylated OCN (PEG-OCN) was well dispersed in water as nanodots with a lateral dimension of approximately 30 nm and a thickness of 0.5-1.2 nm and showed strong photoluminescence in the visible region. Cell-viability testing confirmed that these "heavy-metal-free" organic nanodots were highly biocompatible and noncytotoxic. In particular, the developed nanodots could provide clear confocal images of RAW 264.7 cells without weakening cell activity and displaying any aggregation in a range of concentrations (25-100 µg mL-1 ) with bright-green emission in the cytoplasm.

Production of Metal-Free Composites Composed of Graphite Oxide and Oxidized Carbon Nitride Nanodots and Their Enhanced Photocatalytic Performances.

A novel metal-free composite (GN) composed of two types of carbon-based nanomaterials, graphite oxide (GO) and 2D oxidized carbon nitride (OCN) nanodots was produced. Chemical and morphological characterizations reveal that GN contains a main component of GO with well-dispersed 2D OCN nanodots. GN shows enhanced photocatalytic performance for degrading an organic pollutant, Rhodamine B, under visible light.

Electrochemistry of Layered Graphitic Carbon Nitride Synthesised from Various Precursors: Searching for Catalytic Effects.

Graphitic carbon nitride (g-C3 N4 ), synthesised by pyrolysis of different precursors (dicyandiamide, melamine and urea) under varying reaction conditions (air and nitrogen gas) is subjected to electrochemical studies for the elucidation of the inherent catalytic efficiency of the pristine material. Contrary to popular belief, pristine g-C3 N4 shows negligible, if any, enhancement in its electrochemical behaviour in this comprehensive study. Voltammetric analysis reveals g-C3 N4 to display similar catalytic efficiency to the unmodified glassy carbon electrode surface on which the bulk material was deposited. This highlights the non-catalytic nature of the pristine material and challenges the feasibility of using g-C3 N4 as a heterogeneous catalyst to deliver numerous promised applications.

Thickness-dependent photocatalytic performance of graphite oxide for degrading organic pollutants under visible light.

Photocatalysts use sustainable solar light energy to trigger various catalytic reactions. Metal-free nanomaterials have been suggested as cost-effective and environmentally friendly photocatalysts. In this work, we propose thickness-controlled graphite oxide (GO) as a metal-free photocatalyst, which is produced by exfoliating thick GO particles via stirring and sonication. All GO samples exhibit photocatalytic activity for degrading an organic pollutant, rhodamine B under visible light, and the thickest sample shows the best catalytic performance. UV-vis-NIR diffuse reflectance absorption spectra indicate that thicker GO samples absorb more vis-NIR light than thinner ones. Density-functional theory calculations show that GO has a much smaller band gap than that of single-layer graphene oxide, and thus suggest that the largely-reduced band gap is responsible for this trend of light absorption.

Oxidized carbon nitrides: water-dispersible, atomically thin carbon nitride-based nanodots and their performances as bioimaging probes.

Three-dimensional (3D) carbon nitride (C3 N4 )-based materials show excellent performance in a wide range of applications because of their suitable band structures. To realize the great promise of two-dimensional (2D) allotropes of various 3D materials, it is highly important to develop routes for the production of 2D C3 N4 materials, which are one-atom thick, in order to understand their intrinsic properties and identify their possible applications. In this work, water-dispersible, atomically thin, and small carbon nitride nanodots were produced using the chemical oxidation of graphitic C3 N4 . Various analyses, including X-ray diffraction, X-ray photoelectron, Fourier-transform infrared spectroscopy, and combustion-based elemental analysis, and thermogravimetric analysis, confirmed the production of 3D oxidized C3 N4 materials. The 2D C3 N4 nanodots were successfully exfoliated as individual single layers; their lateral dimension was several tens of nanometers. They showed strong photoluminescence in the visible region as well as excellent performances as cell-imaging probes in an in vitro study using confocal fluorescence microscopy.

Generation of ultra-high-molecular-weight polyethylene from metallocenes immobilized onto N-doped graphene nanoplatelets.

Catalytic natures of organometallic catalysts are modulated by coordinating organic ligands with proper steric and electronic properties to metal centers. Carbon-based nanomaterials such as graphene nanoplatelets are used with and without N-doping and multiwalled carbon nanotube as a ligand for ethylene polymerizations. Zirconocenes or titanocenes are immobilized on such nanomaterials. Polyethylenes (PEs) produced by such hybrids show a great increase in molecular weight relative to those produced by free catalysts. Specially, ultra-high-molecular-weight PEs are produced from the polymerizations at low temperature using the hybrid with N-doped graphene nanoplatelets. This result shows that such nanomaterials act a crucial role to tune the catalytic natures of metallocenes.

Chondrocyte-specific ablation of Osterix leads to impaired endochondral ossification.

Osterix (Osx) is an essential transcription factor required for osteoblast differentiation during both intramembranous and endochondral ossification. Endochondral ossification, a process in which bone formation initiates from a cartilage intermediate, is crucial for skeletal development and growth. Osx is expressed in differentiating chondrocytes as well as osteoblasts during mouse development, but its role in chondrocytes has not been well studied. Here, the in vivo function of Osx in chondrocytes was examined in a chondrocyte-specific Osx conditional knockout model using Col2a1-Cre. Chondrocyte-specific Osx deficiency resulted in a weak and bent skeleton which was evident in newborn by radiographic analysis and skeletal preparation. To further understand the skeletal deformity of the chondrocyte-specific Osx conditional knockout, histological analysis was performed on developing long bones during embryogenesis. Hypertrophic chondrocytes were expanded, the formation of bone trabeculae and marrow cavities was remarkably delayed, and subsequent skeletal growth was reduced. The expression of several chondrocyte differentiation markers was reduced, indicating the impairment of chondrocyte differentiation and endochondral ossification in the chondrocyte-specific Osx conditional knockout. Taken together, Osx regulates chondrocyte differentiation and bone growth in growth plate chondrocytes, suggesting an autonomous function of Osx in chondrocytes during endochondral ossification.

Learning to Forget for Meta-Learning via Task-and-Layer-Wise Attenuation.

Few-shot learning is an emerging yet challenging problem in which the goal is to achieve generalization from only few examples. Meta-learning tackles few-shot learning via the learning of prior knowledge shared across tasks and using it to learn new tasks. One of the most representative meta-learning algorithms is the model-agnostic meta-learning (MAML), which formulates prior knowledge as a common initialization, a shared starting point from where a learner can quickly adapt to unseen tasks. However, forcibly sharing an initialization can lead to conflicts among tasks and the compromised (undesired by tasks) location on optimization landscape, thereby hindering task adaptation. Furthermore, the degree of conflict is observed to vary not only among the tasks but also among the layers of a neural network. Thus, we propose task-and-layer-wise attenuation on the compromised initialization to reduce its adverse influence on task adaptation. As attenuation dynamically controls (or selectively forgets) the influence of the compromised prior knowledge for a given task and each layer, we name our method Learn to Forget (L2F). Experimental results demonstrate that the proposed method greatly improves the performance of the state-of-the-art MAML-based frameworks across diverse domains: few-shot classification, cross-domain few-shot classification, regression, reinforcement learning, and visual tracking.

Cobalt-Based Active Species Molecularly Immobilized on Carbon Nanotubes for the Oxygen Reduction Reaction.

Hybrid systems in which molecule-based active species are combined with nanoscale materials may offer valuable routes to enhance catalytic performances for electrocatalytic reactions. The development of rationally designed, cost-effective, efficient catalysts for the oxygen reduction reaction (ORR) is a crucial challenge for applications in fuel cells and metal-air batteries. A new hybrid ORR catalyst has been synthesized through a well-defined reaction between Co-based organometallic molecules and N-doped multiwalled carbon nanotubes (MWCNTs) at room temperature. The hybrid ORR catalyst shows excellent catalytic performance with an onset potential of 0.95 V [vs. the reversible hydrogen electrode (RHE)], superior durability, and good methanol tolerance. Chemical and structural characterization after many reaction cycles reveals that the Co-based organometallic species maintained the original structure of cobalt(II) acetylacetonate with coordination to the heteroatoms of the MWCNTs. A thorough electrochemical investigation indicates that the major catalytically active site is Co-O4 -NCNT .

Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control.

The high-volume synthesis of two-dimensional (2D) materials in the form of platelets is desirable for various applications. While water is considered an ideal dispersion medium, due to its abundance and low cost, the hydrophobicity of platelet surfaces has prohibited its widespread use. Here we exfoliate 2D materials directly in pure water without using any chemicals or surfactants. In order to exfoliate and disperse the materials in water, we elevate the temperature of the sonication bath, and introduce energy via the dissipation of sonic waves. Storage stability greater than one month is achieved through the maintenance of high temperatures, and through atomic and molecular level simulations, we further discover that good solubility in water is maintained due to the presence of platelet surface charges as a result of edge functionalization or intrinsic polarity. Finally, we demonstrate inkjet printing on hard and flexible substrates as a potential application of water-dispersed 2D materials.

Generation of B-doped graphene nanoplatelets using a solution process and their supercapacitor applications.

Chemically modified graphene (CMG) nanoplatelets have shown great promise in various applications due to their electrical properties and high surface area. Chemical doping is one of the most effective methods to tune the electronic properties of graphene materials. In this work, novel B-doped nanoplatelets (borane-reduced graphene oxide, B-rG-O) were produced on a large scale via the reduction of graphene oxide by a borane-tetrahydrofuran adduct under reflux, and their use for supercapacitor electrodes was studied. This is the first report on the production of B-doped graphene nanoplatelets from a solution process and on the use of B-doped graphene materials in supercapacitors. The B-rG-O had a high specific surface area of 466 m(2)/g and showed excellent supercapacitor performance including a high specific capacitance of 200 F/g in aqueous electrolyte as well as superior surface area-normalized capacitance to typical carbon-based supercapacitor materials and good stability after 4500 cycles. Two- and three-electrode cell measurements showed that energy storage in the B-rG-O supercapacitors was contributed by ion adsorption on the surface of the nanoplatelets in addition to electrochemical redox reactions.

Chemical structures of hydrazine-treated graphene oxide and generation of aromatic nitrogen doping.

Chemically modified graphene platelets, produced via graphene oxide, show great promise in a variety of applications due to their electrical, thermal, barrier and mechanical properties. Understanding the chemical structures of chemically modified graphene platelets will aid in the understanding of their physical properties and facilitate development of chemically modified graphene platelet chemistry. Here we use (13)C and (15)N solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy to study the chemical structure of (15)N-labelled hydrazine-treated (13)C-labelled graphite oxide and unlabelled hydrazine-treated graphene oxide, respectively. These experiments suggest that hydrazine treatment of graphene oxide causes insertion of an aromatic N(2) moiety in a five-membered ring at the platelet edges and also restores graphitic networks on the basal planes. Furthermore, density-functional theory calculations support the formation of such N(2) structures at the edges and help to elucidate the influence of the aromatic N(2) moieties on the electronic structure of chemically modified graphene platelets.

Hypocholesterolemic activity of hesperetin derivatives.

Hesperetin ester and ether derivatives possessing a long alkyl chain were synthesized for examining their hypocholesterolemic activities in high cholesterol-fed mice. Hesperetin 7-O-lauryl ether (4b) and hesperetin 7-O-oleyl ether (4e) exhibited strong cholesterol-lowering effects.

Anti-atherogenic effects of 3,4-Dihydroxy hydrocinnamides.

3,4-Dihydroxy hydrocinnamides 2 and 3 exhibited the anti-atherogenic activities by inhibiting the formation of aortic fatty streak in high cholesterol-fed rabbits.