Size-dependent grain-growth kinetics observed in nanocrystalline Fe

Measurements of grain growth in nanocrystalline Fe reveal a linear dependence of the grain size on annealing time, contradicting studies in coarser-grained materials, which find a parabolic (or power-law) dependence. When the grain size exceeds approximately 150 nm, a smooth transition from linear to nonlinear growth kinetics occurs, suggesting that the rate-controlling mechanism for grain growth depends on the grain size. The linear-stage growth rate agrees quantitatively with a model in which boundary migration is controlled by the redistribution of excess volume localized in the boundary cores.     

trans‐Decahydronaphthalene (decalin) from powder diffraction data

The title compound, C₁₀H₁₈, a decalin stereoisomer, crystallizes with Z′ = 0.5 in the space group P2₁/n. The trans‐decalin molecule is located on an inversion centre with both rings in a chair conformation, making for a quasi‐flat overall shape. Despite the absence of hydrogen bonds, it crystallizes easily. In this work the unknown crystal structure of trans‐decalin has been solved and refined using X‐ray powder diffraction data.     

Overtone spectroscopy of some benzaldehyde derivatives

Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm⁻¹ region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined. We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed in these distances is an indication of the substitution effect. It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the case of o-disubstituted benzenes it is only 80% of the para-substituted shift.     

Crystal microstructure of annealed nanocrystalline Chromium studied by synchrotron radiation diffraction

The microstructure of electrodeposited nanocrystalline chromium (n-Cr) was studied by using synchrotron radiation (SR) diffraction, SEM, TEM, and EDX techniques. The as-prepared n-Cr samples show the standard bcc crystal structure of Cr with volume-averaged column lengths varying from 25 to 30 nm. The grain growth kinetics and the oxidation kinetics were studied by time resolved SR diffraction measurements with n-Cr samples annealed at 400, 600, and 800 °C. The grain growth process is relatively fast and it occurs within the first 10 min of annealing. The final crystallite size depends only on the annealing temperature and not on the initial grain size or on the oxygen content. The final volume-averaged column lengths observed after 50 min annealing are 40(4), 80(1), and 120(2) nm for temperatures 400, 600, and 800 °C, respectively. It is shown that annealing ex situ of n-Cr at 800 °C both under vacuum and in air gives a grain growth process with the same final crystallite sizes. The formation of the Cr₂O₃ and CrH phases is observed during annealing.     

Electroactive planar waveguide studies of Ru(bpy)3(2+) intercalated in a thin clay film: I. Transport and electrochemical phenomena

Electroactive planar waveguide (EAPW) instrumentation was used to perform potential modulated absorbance (PMA) experiments at indium tin oxide (ITO) electrodes coated with 0-, 300-, 800-, and 1200-nm-thick SWy-1 montmorillonite clay. PMA experiments performed at low potential modulation monitor mass transport events within 100 nm of the ITO surface and, thus, when used in conjunction with cyclic voltammetry (CV), can elucidate charge transport mechanisms. The data show that at very thin films electron transfer is controlled by electron hopping (sensitive to the anion species in the electrolyte) in an adsorbed Ru(bpy)(3)(2+) layer. As the thickness of the clay film grows, electron transfer may become controlled by mass transfer of Ru(bpy)(3)(2+) within the clay film to and from the electrode surface, a mechanism that is affected by the swelling of the film. Film swelling is controlled by the cation of the electrolyte. Films loaded with Ru(bpy)(3)(2+) while being subjected to evanescent wave stimulation demonstrate a large hydrophobic layer. The growth of the hydrophobic layer is attributed to the formation of Ru(bpy)(3)(2+*), which has negative charge located at the periphery of the molecule enhancing clay/complex repulsion. The results suggest that the structure of the film and the mechanism of charge transport can be rationally controlled. Simultaneous measurements of the ingress of Ru(bpy)(3)(2+) into the clay film by CV and PMA provide a means to determine the diffusion coefficient of the complex.     

Clays as architectural units at modified-electrodes

Since Ghosh and Bard [80] first established the field of clay-modified electrodes some 15 years ago, great strides have been made in understanding the nature of the clay structural units and their impact on transport of a variety of electroactive probes (anions, neutrals, small cations, large cations, and compounds with distributed charge). Great strides have also been made in understanding the nature of the layered material in creating access of interlayer sites (size, charge, iron content, pillaring, and organic tailoring). In the last five years several successful applications of clay-modified electrodes have been achieved. Given the explosive growth in tailoring and construction of novel clay structures it seems reasonable to predict further significant advances in applications involving clay-modified electrodes.     

Stereocontrolled synthesis of trisubstituted cyclopropanes: expedient, atom-economical, asymmetric syntheses of (+)-Bicifadine and DOV21947

[reaction: see text] An expedient, atom-economical, asymmetric synthesis of 1-aryl-3-azabicyclo[3.1.0]hexanes, including (+)-Bicifadine and DOV21947, in a single-stage through process without isolation of any intermediates has been developed. The key of this synthesis is the in-depth mechanistic understanding of the complicated epoxy nitrile coupling at each reaction stage. Therefore, the desired trisubstituted cyclopropane can be prepared in high ee and yield by controlling the reaction pathway through manipulating the nitrile anion aggregation state.     

Pressure‐Tuneable Visible‐Range Band Gap in the Ionic Spinel Tin Nitride

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high‐pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn₃N₄ under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue‐shift spanning the entire visible spectrum. The pressure‐mediated band gap opening is general to this material across numerous high‐density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure‐tuneable electronic properties for future applications.     

Ultrasound in natural products synthesis: applications to the synthesis of histrionicotoxin via nitroalkanal acetals

Ultrasound promoted the Kornblum reaction of silver nitrite or sodium nitrite with haloalkyl acetals to afford the corresponding C-nitro compounds. The acetalprotected nitro compounds were used as reactants in a 'double Henry' reaction to produce the key intermediate nitrocyclohexane diol with a masked aldehyde side chain. The nitrodiol was then subjected to an ultrasound-promoted one-pot/single operation sequence involving a reduction deprotection followed by a cyclization-reduction. The entire sequence provided the core spiropiperidine substructure of the histrionicotoxins.