V.R. Dhanak

Carbon Nanotubes in Cancer Therapy and Drug Delivery

Carbon nanotubes (CNTs) have been introduced recently as a novel carrier system for both small and large therapeutic molecules. CNTs can be functionalized (i.e., surface engineered) with certain functional groups in order to manipulate their physical or biological properties. In addition to the ability of CNTs to act as carriers for a wide range of therapeutic molecules, their large surface area and possibility to manipulate their surfaces and physical dimensions have been exploited for use in the photothermal destruction of cancer cells. This paper paper will discuss the therapeutic applications of CNTs with a major focus on their applications for the treatment of cancer.

Oxygen and nitrogen interaction with rhodium single crystal surfaces

Abstract Rhodium single crystals show a surprisingly wide range of reconstructions induced by light elements such as oxygen and nitrogen, as well a number of chemical reactions of fundamental chemical importance. In this review, we present and critically discuss the current state of knowledge of the interaction of oxygen, nitrogen and mixed O+N layers with such Rh surfaces, emphasising structural aspects and their impact on the surface reactivity. On the basis of the available experimental results we will elucidate some general trends, which shed light on the possible driving forces behind the diffusive and displacive reconstructions induced by adsorbed atomic oxygen and nitrogen. More attention will be paid to the reconstructive interactions on a Rh(1 1 0) surface. The following three topics are reviewed. The first concerns oxygen interaction with low and some high index Rh surfaces, covering oxygen coverages, adsorption sites, bond strength, ordered structures, sub-surface penetration and oxide formation, and observed by various surface sensitive techniques: X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) 3 , high resolution electron energy loss spectroscopy (HREELS), ultraviolet photoemission spectroscopy (UPS), He scattering, scanning tunneling microscopy (STM), low energy electron diffraction (LEED), etc. They are summarised in a manner illustrating the similarities and differences in oxygen interaction with different Rh single crystal planes. The emphasis is on the reaction conditions when oxygen induces restructuring of the substrate surface. The variety of oxygen-induced (1 × n ) missing/added row reconstructions on the Rh(1 1 0) surface is reviewed and discussed in some detail. Comparison will be made with (1 1 0) surfaces of other Group VIII/IB fcc metals Pd, Cu, Ni and Ag where missing/added row reconstructions are also observed. For Pd, the reconstruction seems similar, whereas for the other three metals it is in a direction orthogonal to that on Rh. In addition, the oxygen on Rh is co-ordinated to three substrate atoms, whereas on Cu, Ni and Ag it is co-ordinated to four atoms.

Electrospray deposition of fullerenes in ultra-high vacuum: in situ scanning tunneling microscopy and photoemission spectroscopy

Electrospray deposition of fullerenes on gold has been successfully observed by in situ room temperature scanning tunneling microscopy and photoemission spectroscopy. Step-edge decoration and hexagonal close-packed islands with a periodicity of 1 nm are observed at low and multilayer coverages respectively, in agreement with thermal evaporation studies. Photoemission spectroscopy shows that fullerenes are being deposited in high purity and are coupling to the gold surface as for thermal evaporation. These results open a new route for the deposition of thermally labile molecules under ultra-high vacuum conditions for a range of high resolution surface science techniques.

Enhanced stab resistance of armor composites with functionalized silica nanoparticles

Traditionally shear thickening fluid (STF) reinforced with Kevlar has been used to develop flexible armor. At the core of the STF-Kevlar composites is a mixture of polyethylene glycol (PEG) and silica particles. This mixture is often known as STF and is consisted of approximately 45 wt % PEG and 55 wt % silica. During rheological tests, STF shows instantaneous spike in viscosity above a critical shear rate. Fabrication of STF-Kevlar composites requires preparation of STF, dilution with ethanol, and then impregnation with Kevlar. In the current approach, nanoscale silica particles were dispersed directly into a mixture of PEG and ethanol through a sonic cavitation process. Two types of silica nanoparticles were used in the investigation: 30 nm crystalline silica and 7 nm amorphous silica. The admixture was then reinforced with Kevlar fabric to produce flexible armor composites. In the next step, silica particles are functionalized with a silane coupling agent to enhance bonding between silica and PEG. The ...

Reactions and luminescence in passivated Si nanocrystallites induced by vacuum ultraviolet and soft-x-ray photons

Alkyl-modified silicon nanocrystallites are efficient fluorophores which are of interest for fundamental spectroscopic studies and as luminescent probes in biology because of their stability in aqueous media. In this work we have investigated these particles using scanning tunneling microscopy, synchrotron-radiation excited photoemission, and x-ray excited optical luminescence (XEOL). During the course of illumination with 145-eV photons we have monitored the evolution of the Si2p core level and, in samples which have suffered prolonged atmospheric exposure, observed in real time the growth of an extra Si2p component attributed to in situ photoinduced oxidation of the Si nanocrystallites. XEOL reveals that two emission bands are active upon soft-x-ray photon excitation and that photoluminescence intensity decreases with photon exposure, which is attributed to charge trapping within the film.

Hydrogen Bond-Induced Pair Formation of Glycine on the Chiral Cu{531} Surface

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and intermolecular interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the case for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

The electronic fine structure of 4-nitrophenyl functionalized single-walled carbon nanotubes.

Controlling the electronic structure of carbon nanotubes (CNTs) is of great importance to various CNT based applications. Herein the electronic fine structure of single-walled carbon nanotube films modified with 4-nitrophenyl groups, produced following reaction with 4-nitrobenzenediazonium tetrafluoroborate, was investigated for the first time. Various techniques such as x-ray and ultra-violet photoelectron spectroscopy, and near edge x-ray absorption fine structure studies were used to explore the electronic structure, and the results were compared with the measured electrical resistances. A reduction in number of the pi electronic states in the valence band consistent with the increased resistance of the functionalized nanotube films was observed.

Finite Size Effects in Magnetic and Optical Properties of Antiferromagnetic NiO Nanoparticles

We report systematic investigations on structural, magnetic and optical properties of NiO nanoparticles prepared by mechanical alloying. As-milled powders exhibit face centred cubic structure, but average particle size decreases and effective strain increases for the initial periods of milling. Lattice volume increases monotonically with a reduction in particle size. Antiferromagnetic NiO particles exhibit significant room temperature (RT) ferromagnetism with modest moment and coercivity. A maximum moment of 0.0147 μB/f.u at 12 kOe applied field and a coercivity of 160 Oe were obtained for 30 h milled NiO powder. Exchange bias decreases linearly with a decrease in NiO particle size. Thermo-magnetization data reveal the presence of mixed magnetic phases in milled powders and shifts magnetic phase transition towards high temperature with increasing milling. Annealing of milled NiO powder and photoluminescence studies show a large reduction in RT magnetic moment and blue-shifting of band edge emission peak. The observed properties are discussed on the basis of finite size effect, defect density, oxidation/reduction of Ni, increase in number of sublattices, uncompensated spins from surface to particle core, and interaction between uncompensated surfaces and particle core with lattice expansion.

Templated quasicrystalline molecular ordering.

Quasicrystals are materials with long-range ordering but no periodicity. We report scanning tunneling microscopy (STM) observations of quasicrystalline molecular layers on 5-fold quasicrystal surfaces. The molecules adopt positions and orientations on the surface consistent with the quasicrystalline ordering of the substrate. Carbon-60 adsorbs atop sufficiently separated Fe atoms on icosahedral Al-Cu-Fe to form a unique quasicrystalline lattice, whereas further C60 molecules decorate remaining surface Fe atoms in a quasi-degenerate fashion. Pentacene (Pn) adsorbs at 10-fold symmetric points around surface-bisected rhombic triacontahedral clusters in icosahedral Ag-In-Yb. These systems constitute the first demonstrations of quasicrystalline molecular ordering on a template.

'Ge interface engineering using ultra-thin La2O3 and Y2O3 films: A study into the effect of deposition temperature'

A study into the optimal deposition temperature for ultra-thin La2O3/Ge and Y2O3/Ge gate stacks has been conducted in this paper with the aim to tailor the interfacial layer for effective passivation of the Ge interface. A detailed comparison between the two lanthanide oxides (La2O3 and Y2O3) in terms of band line-up, interfacial features, and reactivity to Ge using medium energy ion scattering, vacuum ultra-violet variable angle spectroscopic ellipsometry (VUV-VASE), X-ray photoelectron spectroscopy, and X-ray diffraction is shown. La2O3 has been found to be more reactive to Ge than Y2O3, forming LaGeOx and a Ge sub-oxide at the interface for all deposition temperature studied, in the range from 44 °C to 400 °C. In contrast, Y2O3/Ge deposited at 400 °C allows for an ultra-thin GeO2 layer at the interface, which can be eliminated during annealing at temperatures higher than 525 °C leaving a pristine YGeOx/Ge interface. The Y2O3/Ge gate stack deposited at lower temperature shows a sub-band gap absorption f...