K. A. Shiral Fernando

Advances toward bioapplications of carbon nanotubes

Bioapplications of carbon nanotubes have been predicted and explored ever since the discovery of these one-dimensional carbon allotropes. Indeed, carbon nanotubes have many interesting and unique properties potentially useful in a variety of biological and biomedical systems and devices. Significant progress has been made in the effort to overcome some of the fundamental and technical barriers toward bioapplications, especially on issues concerning the aqueous solubility and biocompatibility of carbon nanotubes and on the design and fabrication of prototype biosensors. In this article we take a comprehensive look at the advances in this fast-moving and exciting research field. We review the current status of available methodologies for the aqueous dispersion and solubilization of carbon nanotubes, discuss the results on modifications of carbon nanotubes with various biological and bioactive species, and highlight some of the recent achievements in the fabrication and evaluation of carbon nanotube-based bioanalytical devices.

Carbon Nanoparticles as Visible-Light Photocatalysts for Efficient CO2 Conversion and Beyond

Increasing atmospheric CO(2) levels have generated much concern, driving the ongoing carbon sequestration effort. A compelling CO(2) sequestration option is its photocatalytic conversion to hydrocarbons, for which the use of solar irradiation represents an ultimate solution. Here we report a new strategy of using surface-functionalized small carbon nanoparticles to harvest visible photons for subsequent charge separation on the particle surface in order to drive the efficient photocatalytic process. The aqueous solubility of the catalysts enables photoreduction under more desirable homogeneous reaction conditions. Beyond CO(2) conversion, the nanoscale carbon-based photocatalysts are also useful for the photogeneration of H(2) from water under similar conditions.

Graphene Oxide: A Nonspecific Enhancer of Cellular Growth

There have been multiple conflicting reports about the biocompatibility and antimicrobial activity of graphene oxide. To address this, we conducted a study to characterize the antimicrobial properties of graphene oxide (GO) and its biocompatibility with mammalian cells. When GO was added to a bacterial culture at 25 μg/mL, the results showed that bacteria grew faster and to a higher optical density than cultures without GO. Scanning electron microscopy indicated that bacteria formed dense biofilms in the presence of GO. This was shown by a large mass of aggregated cells and extracellular polymeric material. Bacterial growth on filters coated with 25 and 75 μg of GO grew 2 and 3 times better than on filters without GO. Closer analysis showed that bacteria were able to attach and proliferate preferentially in areas containing the highest GO levels. Graphene oxide films failed to produce growth inhibition zones around them, indicating a lack of antibacterial properties. Also, bacteria were able to grow on GO films to 9.5 × 10(9) cells from an initial inoculation of 1.0 × 10(6), indicating that it also lacks bacteriostatic activity. Thus, silver-coated GO films were able to produce clearing zones and cell death. Also, graphene oxide was shown to greatly enhance the attachment and proliferation of mammalian cells. This study conclusively demonstrates that graphene oxide does not have intrinsic antibacterial, bacteriostatic, and cytotoxic properties in both bacteria and mammalian cells. Furthermore, graphene oxide acts as a general enhancer of cellular growth by increasing cell attachment and proliferation.

Carbon Quantum Dots and Applications in Photocatalytic Energy Conversion

Quantum dots (QDs) generally refer to nanoscale particles of conventional semiconductors that are subject to the quantum-confinement effect, though other nanomaterials of similar optical and redox properties are also named as QDs even in the absence of strictly defined quantum confinement. Among such nanomaterials that have attracted tremendous recent interest are carbon dots, which are small carbon nanoparticles with some form of surface passivation, and graphene quantum dots in various configurations. In this article, we highlight these carbon-based QDs by focusing on their syntheses, on their photoexcited state properties and redox processes, and on their applications as photocatalysts in visible-light carbon dioxide reduction and in water-splitting, as well as on their mechanistic similarities and differences.

Metallic single-walled carbon nanotubes for conductive nanocomposites.

This article reports an unambiguous demonstration that bulk-separated metallic single-walled carbon nanotubes offer superior performance (consistently and substantially better than the as-produced nanotube sample) in conductive composites with poly(3-hexylthiophene) and also in transparent conductive coatings based on PEDOT:PSS. The results serve as a validation on the widely held view that the carbon nanotubes are competitive in various technologies currently dominated by conductive inorganic materials (such as indium tin oxide).

Reversible Accumulation of PEGylated Single-Walled Carbon Nanotubes in the Mammalian Nucleus

Carbon nanotubes (CNTs) have been shown to cross cell membranes and can mediate the internalization of macromolecules. These characteristics have constituted CNTs as an exciting new tool for drug delivery and biological sensing. While CNTs exhibit great potential in biomedical and pharmaceutical applications, neither the cell penetration mechanism of CNTs nor the intracellular fate of the internalized CNTs are fully understood. In this study, time-lapse fluorescence microscopy was used to investigate the intracellular distribution of FITC labeled PEGylated single-walled CNTs (FITC-PEG-SWCNTs) in living cells and shown that PEGylated SWCNTs entered the nucleus of several mammalian cell lines in an energy-dependent process. The presence of FITC-PEG-SWCNTs in the cell nucleus did not cause discernible changes in the nuclear organization and had no effect on the growth kinetics and cell cycle distribution for up to 5 days. Remarkably, upon removal of the FITC-PEG-SWCNTs from the culture medium, the internalized FITC-PEG-SWCNTs rapidly moved out of the nucleus and were released from the cells. Thus, the intracellular PEGylated SWCNTs were highly dynamic and the cell penetration of PEGylated SWCNTs appeared as bidirectional. These observations suggest SWCNTs may be used as an ideal nanovector in biomedical and pharmaceutical applications.

Aqueously Dispersed Silver Nanoparticle-Decorated Boron Nitride Nanosheets for Reusable, Thermal Oxidation-Resistant Surface Enhanced Raman Spectroscopy (SERS) Devices

The impurity-free aqueous dispersions of boron nitride nanosheets (BNNS) allowed the facile preparation of silver (Ag) nanoparticle-decorated BNNS by chemical reduction of an Ag salt with hydrazine in the presence of BNNS. The resultant Ag-BNNS nanohybrids remained dispersed in water, allowing convenient subsequent solution processing. By using substrate transfer techniques, Ag-BNNS nanohybrid thin film coatings on quartz substrates were prepared and evaluated as reusable surface enhanced Raman spectroscopy (SERS) sensors that were robust against repeated solvent washing. In addition, because ofthe unique thermal oxidation-resistant properties of the BNNS, the sensor devices may be readily recycled by short-duration high temperature air oxidation to remove residual analyte molecules in repeated runs. The limiting factor associated with the thermal oxidation recycling process was the Ostwald ripening effect of Ag nanostructures.

Efficient Fluorescence Quenching in Carbon Dots by Surface-Doped Metals - Disruption of Excited State Redox Processes and Mechanistic Implications

The carbon dots in this study were small carbon nanoparticles with the particle surface functionalized by oligomeric poly(ethylene glycol) diamine molecules. Upon photoexcitation, the brightly fluorescent carbon dots in aqueous solution served the function of excellent electron donors to reduce platinum(IV) and gold(III) compounds into their corresponding metals to be deposited on the dot surface. The deposited metals even in very small amounts were found to have dramatic quenching effects on the fluorescence emission intensities, but essentially no effects on the observed fluorescence decays. The obviously exclusive near-neighbor static quenching could be attributed to the disruption of electron-hole radiative recombinations (otherwise responsible for the fluorescence emissions in carbon dots). The results provide important evidence for the availability of photogenerated electrons that could be harvested for productive purposes, which in turn supports the current mechanistic framework on fluorescence emission and photoinduced redox properties of carbon dots.

Solubilization of boron nitride nanotubes

A successful attempt in the functionalization and solubilization of boron nitride nanotubes is reported, and a functionalization mechanism based on interactions of amino functional groups with nanotube surface borons is proposed.

Spontaneous Hydrogen Generation from Organic-Capped Al Nanoparticles and Water

The development of technologies that would lead toward the adoption of a hydrogen economy requires readily available, safe, and environmentally friendly access to hydrogen. This can be achieved using the aluminum-water reaction; however, the protective nature and stability of aluminum oxide is a clear detriment to its application. Here, we demonstrate the spontaneous generation of hydrogen gas from ordinary room-temperature tap water when combined with aluminum-oleic acid core-shell nanoparticles obtained via sonochemistry. The reaction is found to be near-complete (>95% yield hydrogen) with a tunable rate from 6.4x10(-4) to 0.01 g of H2/s/g of Al and to yield an environmentally benign byproduct. The potential of these nanoparticles as a source of hydrogen gas for power generation is demonstrated using a simple fuel cell with an applied load.