NMR spectral studies: XIII—titanium tetrachloride-induced and lanthanide-induced shifts in the proton NMR spectra of β-lactams

2-Azetidinones which carry a proton each on C-3 and C-4 often pose a problem in the correct assignment of the resonances due to these protons; titanium tetrachloride has been shown to be an effective and reliable n.m.r. shift reagent to differentiate between these two protons on the basis of their different sensitivities to this reagent. A few compounds were also studied with Eu(fod)₃ and Pr(fod)₃ for the sake of confirmation.     

Deformation mechanisms of ultra-thin Al layers in Al/SiC nanolaminates as a function of thickness and temperature

The mechanical properties of Al/SiC nanolaminates with layer thicknesses between 10 and 100 nm were studied by nanoindentation in the temperature range 25 to 100 °C. The strength of the Al layers as a function of the layer thickness and temperature was obtained from the hardness of the nanolaminates by an inverse methodology based on the numerical simulation of the nanoindentation tests by means of the finite element method. The room temperature yield stress of the Al layers showed a large ‘the thinner, the stronger’ effect, which depended not only on the layer thickness but also on the microstructure, which changed with the Al layer thickness. The yield stress of the Al layers at ambient temperature was compatible with a deformation mechanism controlled by the interaction of dislocations with grain boundaries for the thicker layers (>50 nm), while confined layer slip appeared to be dominant for layers below 50 nm. There was a dramatic reduction in the Al yield stress with temperature, which increased as the Al layer thickness decreased, and led to an inverse size effect at 100 °C. This behavior was compatible with plastic deformation mechanisms controlled by grain boundary and interface diffusion at 100 °C, which limit the strength of the ultra-thin Al layers.     

Higher isoprenoids—XI: Partial syntheses from cycloartenol,cyclolaudenol—part 3: cyclobuxophyllinine-m,cyclobuxophylline-k and buxanine-m

3β-Acetoxy-9,19-cyclo-4,4,14α-trimethyl-5α-pregnan-20-one, an intermediate readily accessible from cycloartenol/cyclolaudenol has been transformed into cyclobuxophyllinine-M, an alkaloid isolated from certain Buxus Spp. This compound has been earlier converted into the closely related alkaloids cyclobuxophilline-K and buxanine-M. The present work formally constitutes the synthesis of these alkaloids from cycloartenol.     

Ligand Crosslinking Boosts Thermal Transport in Colloidal Nanocrystal Solids

The ongoing interest in colloidal nanocrystal solids for electronic and photonic devices necessitates that their thermal‐transport properties be well understood because heat dissipation frequently limits performance in these devices. Unfortunately, colloidal nanocrystal solids generally possess very low thermal conductivities. This very low thermal conductivity primarily results from the weak van der Waals interaction between the ligands of adjacent nanocrystals. We overcome this thermal‐transport bottleneck by crosslinking the ligands to exchange a weak van der Waals interaction with a strong covalent bond. We obtain thermal conductivities of up to 1.7 Wm^?1 K^?1 that exceed prior reported values by a factor of 4. This improvement is significant because the entire range of prior reported values themselves only span a factor of 4 (i.e., 0.1–0.4 Wm^?1 K^?1). We complement our thermal‐conductivity measurements with mechanical nanoindentation measurements that demonstrate ligand crosslinking increases Young's modulus and sound velocity. This increase in sound velocity is a key bridge between mechanical and thermal properties because sound velocity and thermal conductivity are linearly proportional according to kinetic theory. Control experiments with non‐crosslinkable ligands, as well as transport modeling, further confirm that ligand crosslinking boosts thermal transport.     

Calix[4]arene based molecular probe for sensing copper ions

A novel calix[4]arene based molecular probe for metal ions has been designed, synthesized and evaluated. Studies on its binding with different metal ions reveal a noticeable naked eye color change, bathochromic shift in absorption spectrum and remarkable enhancement in fluorescence emission in the presence of Cu²⁺ only. The role of calix[4]arene scaffold for selective recognition of Cu²⁺ has been demonstrated by repeat evaluation and analysis of an appropriate reference molecule. A rational explanation for fluorescence enhancement in 3 on interaction with copper has been suggested.     

Structural,optical and photoluminescence properties of ZnS: Cu nanoparticle thin films as a function of dopant concentration and quantum confinement effect

Thin films of ZnS: Cu nanoparticles were deposited in chemical bath by a pH controlled solution synthesis technique. The copper concentration was varied from 0 to 0.1M%. XRD and SEM indicated variations in diffracted intensity and morphology with Cu concentration. The PL spectrum of the undoped ZnS nanoparticles showed emission peaks at 393 and 432nm that could be attributed to the intrinsic defect states of ZnS nanoparticles. For ZnS: Cu samples three peaks in the range of 390nm, 480nm and 525nm were observed. With increase in Cu concentration from 0.001 to 0.1M%, the peak position of 480nm and 525nm did not change, whereas 390nm peak red shifted to longer wavelength region to 422nm. In addition, it was found that the overall photoluminescence intensity reached maximum at 0.01M% and quenched with further increase in Cu concentration. Enhancement of blue and green light emission by seven and twenty fivefold respectively compared to undoped ZnS was observed in ZnS: Cu with optimal dopant concentration. Time resolved decay of photoluminescence showed faster decay for 390 – 420nm purple/ blue emission compared to green (525nm) Cu related emission which is in the microsecond time scale. Optical absorption measurements indicate enhancement of band gap (3.89eV) for undoped ZnS suggesting the quantum confinement effect in the developed nanoparticles of size below the Bohr diameter. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Approximation by non-negative algebraic polynomials

Theorem 1 gives an estimate for the approximation of a continuous functionf by polynomials resulting from the convolution off with non-negative algebraic polynomialsp _n . Jackson's theorem can be deduced from it by choosing a particularp _n whose second Chebyshev-Fourier coefficient is sufficiently close to –1.Work supported in part by the Atomic Energy Commission under contract U.S. AEC AT (11-1) 1469, and in part by the National Science Foundation under grant NSF-GJ-812.     

Numerov made explicit has better stability

The well-known two-step fourth order method of Numerov has an interval of periodicity of size 6^1/2; but it is an implicit method. We show the interesting result that if it is made explicit by use of the classical second order method, the resulting method has a larger interval of periodicity of size 12^1/2.     

X-ray,Thermal and Infrared Spectroscopic Studies on Potassium,Rubidium and Caesium Uranyl Oxalate Hydrates

M₂UO₂(C₂O₄)₂⋅nH₂O compounds (M=K, Rb and Cs)have been prepared and characterized by chemical and thermal analyses as well as by X-ray diffraction and infrared spectroscopy. X-ray powder data show that the compounds belong to an orthorhombic system. Thermal and infrared studies show that the compounds decompose to M₂UO₄ through the formation of alkali metal carbonate and UO₂ as intermediates. K₂UO₂(C₂O₄)₂⋅3H₂O, and Rb₂UO₂(C₂O₄)₂⋅2H₂O gave K₂UO₄, Rb₂UO₄ at 700 and 600°C respectively, while in the case of Cs₂UO₂(C₂O₄)₂⋅2H₂O, the intermediate products of decomposition reacted to yield Cs₂U₄O₁₃ at 1000°C. This revised version was published online in July 2006 with corrections to the Cover Date.