Large Area Few-Layer Hexagonal Boron Nitride as a Raman Enhancement Material.

Increasingly, two-dimensional (2D) materials are being investigated for their potential use as surface-enhanced Raman spectroscopy (SERS) active substrates. Hexagonal Boron Nitride (hBN), a layered 2D material analogous to graphene, is mostly used as a passivation layer/dielectric substrate for nanoelectronics application. We have investigated the SERS activity of few-layer hBN film synthesized on copper foil using atmospheric pressure chemical vapor deposition. We have drop casted the probe molecules onto the hBN substrate and measured the enhancement effect due to the substrate using a 532 nm excitation laser. We observed an enhancement of ≈103 for malachite green and ≈104 for methylene blue and rhodamine 6G dyes, respectively. The observed enhancement factors are consistent with the theoretically calculated interaction energies of MB > R6G > MG with a single layer of hBN. We also observed that the enhancement is independent of the film thickness and surface morphology. We demonstrate that the hBN films are highly stable, and even for older hBN films prepared 7 months earlier, we were able to achieve similar enhancements when compared to freshly prepared films. Our detailed results and analyses demonstrate the versatility and durability of hBN films for SERS applications.

Synthesis and characterization of novel protein nanodots as drug delivery carriers with an enhanced biological efficacy of melatonin in breast cancer cells.

Melatonin is a potent antioxidant, chemotherapeutic and chemo preventive agent against breast cancer. However, its short half-life is one of the major limitations in its application as a therapeutic drug. To overcome this issue, the green-emitting protein nanodot (PND) was synthesized by a one-step hydrothermal method for loading melatonin. The synthesized pH-7 and pH-2 PND showed a quantum yield of 22.1% and 14.0%, respectively. The physicochemical characterization of both PNDs showed similar morphological and functional activities. Furthermore, the biological efficacy of melatonin-loaded PND (MPND) was evaluated in a breast cancer cell line (MDA-MB-231) for live-cell imaging and enhanced nano-drug delivery efficacy. Interestingly, the permeability of neutral pH PND in both cell cytoplasm and nucleus nullifies the limitations of real-time live-cell imaging, and ensures nuclear drug delivery efficacy. Neutral pH PND showed better cell viability and cytotoxicity as a fluorescence bioimaging probe compared to acidic PND. The bioavailability and cell cytotoxicity effect of MPND on MDA-MB-231 breast cancer cells were studied through confocal and migration assay. Results showed that MPND causes enhanced bioavailability, better cellular uptake, and inhibition of the migration of breast cancer cells as compared to the drug alone. Besides, the synthesized MPND showed no sign of fluorescence quenching even at a high concentration of melatonin, making it an ideal nanocarrier for bioimaging and drug delivery.

Characterization of Self-Assembled Protein Scaffolds from Collagen-Mimetic Peptides.

Collagen-mimetic peptides have been utilized to form structures of different morphology for various biomedical and nanotechnology applications. This chapter describes the characterization of collagen-mimetic peptide self-assembled structures formed by tuning the interactions between peptides. Inclusion of varying hydrophobicity, electrostatic forces, and stereoselectivity was mainly employed in CMP designs discussed herein. The role of these forces can be assessed using multiple characterization techniques. Light scattering techniques have been employed to study the aggregation kinetics of self-assembled nanostructures and to investigate the net charge distribution of peptides. Spectroscopy techniques like circular dichroism, fluorescence, and absorption spectroscopy have been utilized to decipher the secondary structures of peptide and binding of the peptides with dyes. Imaging techniques helped in resolving the morphology of the self-assembled structures. Confocal fluorescence microscopy and differential scanning calorimetry helped in indirect assessment of hydrophobicity and X-ray studies to determine the inter-helical spacing between the triple helical peptides of the higher order structures.

Templating of arrays of Ru nanoclusters by monolayer graphene/Ru Moirés with different periodicities.

We have studied the formation of Ru nanocluster arrays on several monolayer graphene/Ru Moiré structures with different relative orientations of the graphene and Ru lattices. Experiments and ab initio calculations clearly show that the presence of a graphene/Ru Moiré does not guarantee the ordered adsorption of Ru nanoclusters. The simultaneous deposition of Ru onto coexisting Moirés demonstrates that a structure with aligned graphene and Ru lattices templates the formation of arrays of small Ru clusters with narrow size spread and adsorption exclusively in a single site (the 'low fcc' site). The other Moirés considered here gave rise to substantially larger clusters with broader size distribution and without detectable site selectivity. Calculations explain these findings via the density of states (DOS) at different sites of the graphene/Ru Moiré. The ordered nucleation of many small clusters instead of incorporation of metal atoms into larger ones requires one Moiré site with a large DOS at the Fermi level, so that the binding of metal adatoms to this site is stronger than to competing sites in the Moiré and to existing metal clusters.

Chemical vapor deposition and etching of high-quality monolayer hexagonal boron nitride films.

The growth of large-area hexagonal boron nitride (h-BN) monolayers on catalytic metal substrates is a topic of scientific and technological interest. We have used real-time microscopy during the growth process to study h-BN chemical vapor deposition (CVD) from borazine on Ru(0001) single crystals and thin films. At low borazine pressures, individual h-BN domains nucleate sparsely, grow to macroscopic dimensions, and coalescence to form a closed monolayer film. A quantitative analysis shows borazine adsorption and dissociation predominantly on Ru, with the h-BN covered areas being at least 100 times less reactive. We establish strong effects of hydrogen added to the CVD precursor gas in controlling the in-plane expansion and morphology of the growing h-BN domains. High-temperature exposure of h-BN/Ru to pure hydrogen causes the controlled edge detachment of B and N and can be used as a clean etching process for h-BN on metals.

Graphene growth on Ni(111) by transformation of a surface carbide.

A novel growth mechanism of graphene on Ni(111) has been discovered that occurs at temperatures below 460 °C. At these conditions, a surface-confined nickel-carbide phase coexists with single layer graphene. The graphene grows by in-plane transformation of the carbide along a one-dimensional phase-boundary, which is distinctively different from known growth processes on other transition metals and on Ni above 460 °C, where carbon atoms attach to "free" edges of graphene islands.

An extended defect in graphene as a metallic wire.

Many proposed applications of graphene require the ability to tune its electronic structure at the nanoscale. Although charge transfer and field-effect doping can be applied to manipulate charge carrier concentrations, using them to achieve nanoscale control remains a challenge. An alternative approach is 'self-doping', in which extended defects are introduced into the graphene lattice. The controlled engineering of these defects represents a viable approach to creation and nanoscale control of one-dimensional charge distributions with widths of several atoms. However, the only experimentally realized extended defects so far have been the edges of graphene nanoribbons, which show dangling bonds that make them chemically unstable. Here, we report the realization of a one-dimensional topological defect in graphene, containing octagonal and pentagonal sp(2)-hybridized carbon rings embedded in a perfect graphene sheet. By doping the surrounding graphene lattice, the defect acts as a quasi-one-dimensional metallic wire. Such wires may form building blocks for atomic-scale, all-carbon electronics.

Photocatalytic degradation of methyl orange over single crystalline ZnO: orientation dependence of photoactivity and photostability of ZnO.

The photocatalytic destruction of methyl orange in aqueous solution has been studied over single crystal ZnO surfaces under UV irradiation. Differences in the apparent reaction rates between the polar surfaces (first order) and the nonpolar ZnO(10-10) surface (zero order) were observed. Reaction rates for different crystallographic orientations showed the highest activity for ZnO(10-10) followed by ZnO(0001)-Zn and the lowest activity for ZnO(000-1)-O surfaces. In addition, the etching of surfaces by photolysis has been studied. For this process, strongly face-dependent behavior was also observed. Possible reasons for the face dependencies are discussed.