Effects of substrate shape, curvature and roughness on thin heteroepitaxial films of Pt on Au(1 1 1)

The growth of thin (1–10 nm) films of Pt on Au(1 1 1) was studied in order to understand and clarify differences in growth mode observed in ultra-high vacuum (UHV) studies and in electrochemical deposition studies. It was found that on flat Au(1 1 1), Pt grows in a layer-by-layer growth mode, but if the gold substrate is exposed to an acidic environment prior to Pt deposition, then the substrate becomes nanoscopically rough (islanded) and Pt growth follows a pseudo-Stranski–Krastanov (SK) growth mode in which an initially thin wetting layer becomes rougher with increasing film thickness. An analysis of curvature effects on epitaxial growth mode shows that thermodynamic curvature effects involving surface stress are negligible for the Pt/Au(1 1 1) system. Rather, the apparent SK growth is linked to kinetic effects associated with inhomogeneous in-plane elastic relaxation of Pt films on rough surfaces that drive Pt atoms from pits to the tops of islands in the early stages of growth. Implications for the control of epitaxial film roughness are discussed.     

UTILIZATION OF TOOLS FOR SUCCESSFUL. TROUBLESHOOTING OF STRUCTURAL PROBLEMS

A structural failure problem was solved using an integrated and iterative program of testing and analysis. The steps taken in solving the problem were: analytical calculations; operational testing; qualifications of analytical results; problem identification; design of corrective action; and confirmatory testing.     

A quick method for the determination of the Al/Si weight ratio in alumino-silicates using an Am-Be neutron source

An irradiation procedure with fast and thermal neutrons from a 5 Ci Am-Be isotopic neutron source irradiation facility in combination with a 3'3' NaI(Tl) detector system has been used to determine Al/Si weight ratios in alumino-silicates. Samples were irradiated with and without Cd cover for 10 minutes and counted for 10 minutes after a waiting time of 1 minute. The peak area analysis of the 1779 keV gamma-ray line of ²⁸Al product radionuclide produced via ²⁷Al(n,γ)²⁸Al and ²⁸Si(n,p)²⁸Al reactions in combination with the neutron flux parameter at the irradiation site and nuclear data were used to determine Al/Si ratios. Due to discrepancy in literature data, Am-Be neutron source spectrum averaged cross sections of (n,p) reactions on ²⁷Al, ²⁸Si and ⁵⁶Fe were determined by the activation technique using ¹¹⁵In(n,n')^115mIn as the fast neutron flux monitor reaction. The method was tested using mixtures of high-purity Al₂O₃ and SiO₂ with known weight ratios of Al/Si and validated by a certified reference material BCS-CRM 348 (Ball Clay). Results are presented for bentonite, kaolin, bauxite, feldspar and ball clay samples from Nigeria. The method is non-destructive, rapid and suitable for use in-situ for large-scale exploration works and industrial process control. This revised version was published online in July 2006 with corrections to the Cover Date.     

Functional Nanopores Enabled with DNA

Membrane-spanning nanopores are used in label-free single-molecule sensing and next-generation portable nucleic acid sequencing, and as powerful research tools in biology, biophysics, and synthetic biology. Naturally occurring protein and peptide pores, as well as synthetic inorganic nanopores, are used in these applications, with their limitations. The structural and functional repertoire of nanopores can be considerably expanded by functionalising existing pores with DNA strands and by creating an entirely new class of nanopores with DNA nanotechnology. This review outlines progress in this area of functional DNA nanopores and outlines developments to open up new applications.     

Transient topographies of ion patterned Si(111)

The surface of high fluence ion-sputtered Si(111) was found to exhibit a rich variety of transient one- and two-dimensional topographies that may be exploited as tunable self-organized arrays of nanostructures. Such transient effects are only partially described by analytical models of sputter patterning. However, a discrete atom kinetic Monte Carlo simulation model incorporating curvature-dependent sputtering and surface diffusion reproduces many aspects of the transient morphological evolution, and clarifies the minimal model of sputter patterning.     

The Self‐Assembly of Anticancer Camptothecin–Dipeptide Nanotubes: A Minimalistic and High Drug Loading Approach to Increased Efficacy

20‐(S)‐Camptothecin (CPT)‐conjugated dipeptides are reported that preassemble into nanotubes with diameters ranging from 80–120 nm. These nanoassemblies maintain a high (～47 %) drug loading and exhibit greater drug stability (i.e., resistance to lactone hydrolysis), and consequently greater efficacy against several human cancer cells (HT‐29, A549, H460, and H23) in vitro compared with the clinically used prodrug irinotecan. A key and defining feature of this system is the use of the CPT‐conjugated dipeptide as both the drug and precursor to the nanostructured carrier, which simplifies the overall fabrication process.     

Electronic structure of the water oxidation catalyst cis,cis-[(bpy)2(H2O)Ru(III)ORu(III)(OH2)(bpy)2]4+, the blue dimer

The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.     

Quantitative investigations of aggregate systems

Nanomaterials with disordered, ramified structure are increasingly being used for applications where low cost and enhanced performance are desired. A particular example is the use in printed electronics of inorganic conducting and semiconducting nanoparticles. The electrical, as well as other physical properties depend on the arrangement and connectivity of the particles in such aggregate systems. Quantification of aggregate structure and development of structure∕property relationships is difficult and progress in the application of these materials in electronics has mainly been empirical. In this paper, a scaling model is used to parameterize the structure of printed electronic layers. This model has chiefly been applied to polymers but surprisingly it shows applicability to these nanolayers. Disordered structures of silicon nanoparticles forming aggregates are investigated using small angle x-ray scattering coupled with the scaling model. It is expected that predictions using these structural parameters can be made for electrical properties. The approach may have wide use in understanding and designing nano-aggregates for electronic devices.