Salient features of the aza-Wacker cyclization reaction

The intramolecular aza-Wacker reaction has unparalleled potential for the site-selective amination of olefins, but it is perhaps underappreciated relative to other alkene oxidations. The first part of this review makes the distinction between classical and tethered aza-Wacker cyclization reactions and summarizes examples of the latter. The second portion focuses on developments in asymmetric aza-Wacker cyclization technology. The final part of the review summarizes applications of all classes of aza-Wacker cyclization reactions to natural product assembly.

The aza-Wacker cyclization reaction is a powerful strategy for alkene amination.     

A multi-scale Monte Carlo study of oxide structures on the Cu(1 0 0) surface

We present a multi-scale Monte Carlo study of the oxidation of the Cu(1 0 0) surface based on the Bortz-Kalos-Lebowitz model with the equilibrium energetics obtained from ab initio calculations. The radial and island size distribution functions are examined and Cu-O structures are analyzed at different temperatures and coverages. We concentrate on the coverages of 0.3 monolayer O or less, with variable sub-monolayer coverages of Cu. The results show that even though the ab initio calculations yield a higher barrier for O than for Cu adatom diffusion on Cu(1 0 0), the stability of Cu structures causes the O adatoms to be more mobile on the Cu(1 0 0) surface than the Cu adatoms. We are able to reproduce the c(2 × 2)-O domains seen in the experiments. However, we give an alternative explanation based on the repulsive interactions of O that, on one hand, cause the local ordering and, on the other hand, prohibits large well-ordered domains. We also give interpretation on the formation of the R45°-O reconstruction of Cu(1 0 0) above the O coverages of 0.3 monolayer based on the ab initio energetics.     

Differential and total ionization cross sections due to impact of swift heavy ions

In the present work, the Binary stopping power theory was used to calculate total ionization cross section and differential cross section for energy transfer from a swift heavy ion to the target electrons. The dependence on the projectile charge state is studied. The calculated values are compared with the experimental values collected from the literature.     

Submonolayer growth with anomalously high island density in hyperthermal deposition

We present a rate equation model for submonolayer island growth under conditions where hyperthermal deposition techniques such as low-energy ion deposition are employed to achieve smooth layer-by-layer growth. By asymptotic analysis, we demonstrate that the model exhibits stationary behavior with well-defined dynamic and growth exponents beta and chi, respectively, in the limit of small and high detachment rates. We verify these predictions by using the particle coalescence simulation method. The simulations reveal the existence of a relatively sharp transition regime with an increasing detachment rate of adatoms from high values of the growth exponent beta approximately 1 to much smaller values of beta determined by detachment and island diffusion processes. Our numerical results for the island size distribution indicate an anomalously high number of small islands, in agreement with available experimental data.     

Revealing the Crystal Structure of Anhydrous Calcium Oxalate,Ca[C2O4], by a Combination of Atomistic Simulation and Rietveld Refinement

The existence of three different modifications of anhydrous calcium oxalate is reported since decades. Their crystal structures, however, remained unclear, yet. In the present work the crystal structure of the so‐called β‐modification was revealed by a combination of atomistic computer simulations and Rietveld refinements of the X‐ray powder pattern. No indication for polymorphism was obtained.     

Mimicking the growth of a pathologic biomineral: shape development and structures of calcium oxalate dihydrate in the presence of polyacrylic acid

The morphogenesis of calcium oxalate hydrates in aqueous solutions was investigated by varying the pH, oxalate concentration, and the concentration of the sodium salt of polyacrylate (PAA). With increasing amounts of PAA in solution, the shape of tetragonal calcium oxalate dihydrate (COD) changes from bipyramidal through elongated bipyramidal prisms to dumbbells and finally reverts to rodlike tetragonal bipyramidal prisms. PAA is incorporated into the prismatic zones of the growing COD crystals, thereby reducing the growth rate of the {100} faces along the <100> direction. Dumbbells start to develop through "non-crystallographic" branching from the prism faces and the formation of "multiple head" crystals. Adsorption of PAA on the rough surfaces of the splitting individuals supports the selection of new subindividuals and leads to the formation of core-shell patterns. The various shapes and structures of the biomimetic COD/PAA crystals and aggregates are closely related to the well-known "pathologic" individuals observed in the urine of patients with urinary disease (including urinary stones).     

Changes in Structural and Optical Properties of Polycarbonate Induced by Ag+ Ion Implantation

Transparent polycarbonate samples were implanted with 1 MeV Ag⁺ ions to various doses ranging from 5 × 10¹⁴ to 3 × 10¹⁶ ions cm^?2 with a beam current density of 900 nA cm^?2. Modification in the structure of polycarbonate as a function of the implantation fluence was investigated using micro-Raman spectroscopy, glancing angle X-ray diffraction, and UV-Vis spectroscopy. Raman spectroscopy pointed toward the formation of graphite structures/clusters due to the ion implantation. UV-Vis absorption analysis suggests the formation of a carbonaceous layer and a drastic decrease in optical band gap from 4.12 eV to 0.50 eV at an implanted dose of 3 × 10¹⁶ ions cm^?2. The correlation between the decrease in band gap and the structural changes is discussed.     

Instability and wavelength selection during step flow growth of metal surfaces vicinal to fcc(001)

We study the onset and development of ledge instabilities during growth of vicinal metal surfaces using kinetic Monte Carlo simulations. We observe the formation of periodic patterns at [110] close packed step edges on surfaces vicinal to fcc(001) under realistic molecular beam epitaxy conditions. The corresponding wavelength and its temperature dependence are studied in detail. Simulations suggest that the ledge instability on fcc(1,1,m) vicinal surfaces is controlled by the strong kink Ehrlich-Schwoebel barrier, with the wavelength determined by dimer nucleation at the step edge. Our results are in agreement with recent continuum theoretical predictions, and experiments on Cu(1,1,17) vicinal surfaces.     

Size selected growth of nanodots: effects of growth kinetics and energetics on the formation of stationary size distributions

The size selection of nanodots during the growth is studied by using a reaction kinetic model, where reaction rates depend on the dot size. The characteristic feature of the reaction rates is the energetics, where the free energy of dots has a minimum at the certain dot size. The model equations are solved by using a particle coalescence simulation method. We find phenomenologically three distinct stages of growth. First, during the initial deposition stage, distributions with high density of small dots occur. Second, there is an intermediate and short-lived stationary state, which is controlled by kinetics of growth. Third, a long-lived stationary state is obtained, with nearly Gaussian size distributions, mostly determined by the energetics of the growth but also significantly affected by the kinetics. In the final stage, size selection and narrowing of the distributions occur. It is also shown that in the final stage of growth the Fokker-Planck type continuum model describes well the evolution of the distributions and the size selection.     

N+ Implantation-Induced Surface Hardening of Poly (Allyl Diglycol Carbonate) Polymer

The effect of 100 keV N⁺ ions implantation on the surface structure and hardness of poly (allyl diglycol carbonate) (CR-39) polymer was studied. The surface hardness of virgin and implanted CR-39 specimens was determined using a Knoop microhardness test. The surface hardness was found to be enhanced after implantation, e.g., becoming eight times higher at a load of 9.8 mN, for a dose of 2 × 10¹⁶ ions cm^?2. The change in bonding and surface structure of the CR-39 polymer due to implantation was studied using the specular reflectance Fourier transform infrared (FTIR) technique. The disordering produced in the implanted matrix was estimated using the Urbach edge method from the UV-Visible absorption spectra. The relationship of surface hardening with the chemical and structural changes was explored