Visible-light-driven dynamic cancer therapy and imaging using graphitic carbon nitride nanoparticles.

Organic graphitic carbon nitride nanoparticles (NP-g-CN), less than 30 nm in size, were synthesized and evaluated for photodynamic therapy (PDT) and cell imaging applications. NP-g-CN particles were prepared through an intercalation process using a rod-like melamine-cyanuric acid adduct (MCA) as the molecular precursor and a eutectic mixture of LiCl-KCl (45:55 wt%) as the reaction medium for polycondensation. The nano-dimensional NP-g-CN penetrated the malignant tumor cells with minimal hindrance and effectively generated reactive oxygen species (ROS) under visible light irradiation, which could ablate cancer cells.

Three-dimensional macroscopic assemblies of low-dimensional carbon nitrides for enhanced hydrogen evolution.

Simple organic cooperative assembly of triazine molecules leads to three-dimensional macroscopic assemblies of low-dimensional graphitic carbon nitrides (g-CNs), for example, nanoparticles, nanotubes, and nanosheets. The approach enables the characterization of the cooperative properties and photocatalytic activities of low-dimensional g-CN materials in hydrogen evolution reactions from water under visible light.

Controlled assembly of graphene oxide nanosheets within one-dimensional polymer nanostructure.

We have demonstrated that the location and distribution of graphene oxide nanosheets (GONs) confined in 1D polymer composites were readily controlled depending on the processing conditions of electrospinning such as the types of polymers and the solvents used for the fabrication. The uniform bead-free poly(vinyl alcohol) (PVA)/GON composite nanofibers (NFs) even at high GON loading were obtained from the homogeneous polymer solutions attributable to the favorable interactions, as elucidated by spectroscopic data, thereby showing significant enhancement of their physical properties. The GONs were localized in the surface regions of the PVA-NFs due to the rapid convective evaporation of the water molecules, with concomitant aggregation into several sheets (<10 layers).

Electroactive nanoparticle directed assembly of functionalized graphene nanosheets into hierarchical structures with hybrid compositions for flexible supercapacitors.

Hierarchical structures of hybrid materials with the controlled compositions have been shown to offer a breakthrough for energy storage and conversion. Here, we report the integrative assembly of chemically modified graphene (CMG) building blocks into hierarchical complex structures with the hybrid composition for high performance flexible pseudocapacitors. The formation mechanism of hierarchical CMG/Nafion/RuO2 (CMGNR) microspheres, which is triggered by the cooperative interplay during the in situ synthesis of RuO2 nanoparticles (NPs), was extensively investigated.

Electrochemical assembly of MnO₂ on ionic liquid-graphene films into a hierarchical structure for high rate capability and long cycle stability of pseudocapacitors.

Hierarchical nanostructures are of prime importance due to their large surface area, easy accessibility to reaction sites, fast ion and electron transport, and mechanical integrity. Herein, we demonstrate the synthesis of hierarchically structured MnO₂/ionic liquid-reduced graphene oxide (IL-RGO) nanocomposites through the electrochemical self-assembly. The structures of MnO₂/IL-RGO nanocomposites and their formation mechanism are investigated by spectroscopic methods and as a consequence, correlated with the electrochemical behaviours.

High performance of a solid-state flexible asymmetric supercapacitor based on graphene films.

Solid-state flexible energy storage devices hold the key to realizing portable and flexible electronic devices. Achieving fully flexible energy storage devices requires that all of the essential components (i.e.

3D macroporous graphene frameworks for supercapacitors with high energy and power densities.

In order to develop energy storage devices with high power and energy densities, electrodes should hold well-defined pathways for efficient ionic and electronic transport. Herein, we demonstrate high-performance supercapacitors by building a three-dimensional (3D) macroporous structure that consists of chemically modified graphene (CMG). These 3D macroporous electrodes, namely, embossed-CMG (e-CMG) films, were fabricated by using polystyrene colloidal particles as a sacrificial template.

A fluorescent sensor for selective detection of cyanide using mesoporous graphitic carbon(IV) nitride.

A turn-on fluorescence sensor, Cu(2+)-c-mpg-C(3)N(4), was developed for detection of CN(-) in aqueous solution by simply mixing cubic mesoporous graphitic carbon nitride (c-mpg-C(3)N(4)) and aqueous solution of Cu(NO(3))(2). The highly sensitive detection of CN(-) with a detection limit of 80 nM is not only possible in aqueous solution but also in human blood serum.

Study on the water flooding in the cathode of direct methanol fuel cells.

Water flooding phenomena in the cathode of direct methanol fuel cells were analyzed by using electrochemical impedance spectroscopy. Two kinds of commercial gas diffusion layers with different PTFE contents of 5 wt% (GDL A5) and 20 wt% (GDL B20) were used to investigate the water flooding under various operating conditions. Water flooding was divided into two types: catalyst flooding and backing flooding.

Charge transfer interactions between conjugated block copolymers and reduced graphene oxides.

The charge transfer interactions between reduced graphene oxides and conjugated block copolymers were confirmed by various spectroscopic methods, giving rise to manipulation of the electrical properties of the former.

Facilitated ion transport in all-solid-state flexible supercapacitors.

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.

Programmable peptide-directed two dimensional arrays of various nanoparticles on graphene sheets.

In this research, we report an innovative, chemical strategy for the in situ synthesis and direct two-dimensional (2D) arraying of various nanoparticles (NPs) on graphenes using both programmed-peptides as directing agents and graphenes as pre-formed 2D templates. The peptides were designed for manipulating the enthalpic (coupled interactions) constraint of the global system. Along with the functionalization of graphene for the stable dispersion, peptides directed the growth and array of NPs in a controllable manner.

Site-specific immobilization of gold binding polypeptide on gold nanoparticle-coated graphene sheet for biosensor application.

The effective and strong immobilization of enzymes on solid surfaces is required for current biological applications, such as microchips, biofuel cells, and biosensors. Gold-binding polypeptide (GBP), a genetically designed peptide, possesses unique and specific interactions with a gold surface, resulting in improved enzyme stability and activity. Herein we demonstrated an immobilization method for biosensor applications through site-specific interactions between GBP-fused organophosphorus hydrolase (GBP-OPH) and gold nanoparticle-coated chemically modified graphene (Au-CMG), showing enhanced sensing capability.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters.

Microwave-assisted synthesis of highly water-soluble graphene towards electrical DNA sensor.

Graphene sheets have the potential for practical applications in electrochemical devices, but their development has been impeded by critical problems with aggregation of graphene sheets. Here, we demonstrated a facile and bottom-up approach for fabrication of DNA sensor device using water-soluble sulfonated reduced graphene oxide (SRGO) sheets via microwave-assisted sulfonation (MAS), showing enhanced sensitivity, reliability, and low detection limit. Key to achieving these performances is the fabrication of the SRGOs, where the MAS method enabled SRGOs to be highly dispersed in water (10 mg mL(-1)) due to the acidic sulfonated groups generated within 3 min of the functionalization reaction.

Immobilization of genetically engineered fusion proteins on gold-decorated carbon nanotube hybrid films for the fabrication of biosensor platforms.

We have demonstrated the fabrication of the biosensor platforms by means of the integration of the genetically engineered fusion proteins and the uniform gold nanoparticle-deposited multi-walled nanotube hybrid (Au-MWNT-HB) films for the detection of C-reactive protein (CRP). Au-MWNT-HB films were used as a good electrochemical transducer due to their excellent electrical properties and large surface areas for the signal transduction, while the genetically engineered fusion proteins, or 6His-GBP-SpA fusion proteins, specifically bind onto the surface of the Au-MWNT-HB films and efficiently immobilize bioreceptors for the detection of CRP. As-obtained biosensor platforms were characterized by electrochemical and optical analysis and revealed better performance compared to conventional Au-based biosensors.

Rapid separation of bacteriorhodopsin using a laminar-flow extraction system in a microfluidic device.

A protein separation technology using the microfluidic device was developed for the more rapid and effective analysis of target protein. This microfluidic separation system was carried out using the aqueous two-phase system (ATPS) and the ionic liquid two-phase system (ILTPS) for purification method of the protein sample, and the three-flow desalting system was used for the removal of salts from the sucrose-rich sample. Partitioning of the protein sample was observed in ATPS or ILTPS with the various pHs.

Solution chemistry of self-assembled graphene nanohybrids for high-performance flexible biosensors.

We report the preparation of free-standing flexible conductive reduced graphene oxide/Nafion (RGON) hybrid films by a solution chemistry that utilizes self-assembly and directional convective-assembly. The hydrophobic backbone of Nafion provided well-defined integrated structures, on micro- and macroscales, for the construction of hybrid materials through self-assembly, while the hydrophilic sulfonate groups enabled highly stable dispersibility ( approximately 0.5 mg/mL) and long-term stability (2 months) for graphene.

Spectroscopic and computational insight into the intermolecular interactions between Zwitter-type ionic liquids and water molecules.

Geometric and conformational changes of zwitter-type ionic liquids (ZILs) due to hydrogen-bonding interactions with water molecules are investigated by density functional theory (DFT), two-dimensional IR correlation spectroscopy (2D IR COS), and pulsed-gradient spin-echo NMR (PGSE NMR). Simulation results indicate that molecular structures in the optimized states are strongly influenced by hydrogen bonding of water molecules with the sulfonate group or imidazolium and pyrrolidinium rings of 3-(1-methyl-3-imidazolio)propanesulfonate (1) and 3-(1-methyl-1-pyrrolidinio)propanesulfonate (2), respectively. Concentration-dependent 2D IR COS reveals kinetic conformational changes of the two ZIL-H(2)O systems attributable to intermolecular interactions, as well as the interactions of sulfonate groups and imidazolium or pyrrolidinium rings with water molecules.

Energy transfer in ionic-liquid-functionalized inorganic nanorods for highly efficient photocatalytic applications.

Energy transfer in self-assembled ionic liquids (ILs) and iron oxyhydroxide nanocrystals and the controlled surface chemistry of functionalized nanomaterials for photocatalytic applications are reported. Self-assembled ILs play the role of multifunctional materials in terms of constructing a well-designed nanostructure, controlling the surface chemistry, and triggering the energy transfer of functionalized materials. IL-functionalized beta-FeOOH nanorods show approximately 10-fold higher performances than those of commercial materials due to the synergistic effect of well-defined nanomaterials in diffusion-controlled reactions, specific interactions with target pollutants, and energy transfers in hybrid materials.

Tracking the transition behavior and dynamics of ionic transport in crystalline ionic gel electrolytes.

The transition behavior and dynamics of ionic transport were strongly influenced by changes in the crystal structure and interaction field of the crystalline ionic gel electrolytes with respect to chemical compositions, as proven by impedance, (7)Li NMR, PCA and 2D IR COS.

Green one-pot assembly of iron-based nanomaterials for the rational design of structure.

Green one-pot solution chemistry described herein could delicately manipulate the size and shape of iron oxyhydroxide nanocrystals, even in the aqueous phase, and easily derive a family of iron-based nanomaterials.

Ionic-liquid-assisted sonochemical synthesis of carbon-nanotube-based nanohybrids: control in the structures and interfacial characteristics.

A versatile, facile, and rapid synthetic method of advanced carbon nanotube (CNT)-based nanohybrid fabrication, or the so-called ionic-liquid-assisted sonochemical method (ILASM), which combines the supramolecular chemistry between ionic liquids (ILs) and CNTs with sonochemistry for the control in the size and amount of uniformly decorated nanoparticles (NPs) and interfacial engineering, is reported. The excellence in electrocatalysis of hybrid materials with well-designed nanostructures and favorable interfaces is demonstrated by applying them to electrochemical catalysis. The synthetic method discussed in this report has an important and immediate impact not only on the design and synthesis of functional hybrid nanomaterials by supramolecular chemistry and sonochemistry but also on applications of the same into electrochemical devices such as sensors, fuel cells, solar cells, actuators, batteries, and capacitors.

Clean and facile solution synthesis of iron(III)-entrapped gamma-alumina nanosorbents for arsenic removal.

Iro (III)-entrapped gamma-alumina nanosorbents were prepared by an environmentally benign method using an ionothermal process based on an ionic liquid to synthesize the gamma-alumina host and a sonochemical method to entrap the iron(III) guest. The morphology of the alumina depends on the aluminum precursor used, giving aligned bundled and randomly debundled gamma-alumina nanorods as well as wormlike mesoporous alumina. In particular, the rodlike structure shows significantly greater mesoporosity than the wormlike porous gamma-alumina structure.