Correlating fast and slow chemical shift spinning sideband patterns in solid-state NMR

An experiment is presented that enables the measurement of small chemical shift anisotropy tensors under fast magic-angle spinning (MAS). The two-dimensional spectra obtained give a fast MAS sideband pattern in the directly observed dimension with the spinning sideband intensities equivalent to the chemical shift anisotropy scaled by a factor of N, or equivalently the sample spinning frequency scaled by 1/N, in the indirectly observed dimension. The scaling factor may be arbitrarily varied by changing the number and timings of the rotor synchronized pi-pulses used. Desirable features of the experiment include a fixed length pulse sequence and efficient sampling of the indirectly observed dimension. In addition, neither quadrature detection in the indirect dimension nor storage periods are required, consequently no signal intensity is discarded by the pulse sequence. The experiment is demonstrated using (31)P NMR of sodium phosphate and (13)C NMR of fumaric acid monoethyl ester for which a scaling factor of N=10.2 was employed.     

Competitive electron transfers from a tyrosyl side-chain and peptide bond in the photodegradation of N-tosyl alpha-aminomethylamides: an insight into photosynthesis and photodamage in the biological oxidation of water?

Photo-excited N-tosyl derivatives of phenylalanyl- and, more particularly, O-methyltyrosylmethylamides undergo electron transfer from aryl to tosyl groups whereas the photo-degradation of aliphatic analogues is initiated by electron transfer from the peptide bond, suggesting the latter as one possible reason for the rapid turnover of the D1 protein in biological water oxidation when the essential mediating role of tyrosine 116 in the PSII complex is inhibited.     

4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes from the cane beetle antitrogusparvulus--cuticular hydrocarbons with unprecedented structure and stereochemistry

The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus were deduced to be 4,6,8,10,16,18-hexa- and 4,6,8,10,16-pentamethyldocosanes 2 and 3, respectively. Isomers of 2,4,6,8-tetramethylundecanal 27, 36, and 37, derived from 2,4,6-trimethylphenol, were coupled with the phosphoranes 28 and 29 to furnish alkenes and, by reduction, diastereomers of 2 and 3. Chromatographic and spectroscopic comparisons confirmed 2 as either 6a or 6b and 3 as either 34a or 34b. [structure: see text]     

Use of silica gels and mesoporous molecular sieves as supports for the solid-phase Claisen rearrangement

A series of silica gels and mesoporous molecular sieves differing in both the range of particle size and mean pore size were derivatized with the p-[(R,S)-α-[1-(9H-fluoren-9-yl)-methoxyformamido]-2,4-dimethoxybenzyl]-p henoxyacetic acid linker and their loading capacities were measured. Loading capacities ranging between 0.4–0.6 mmol Fmoc/g were achieved. Several of these silica based materials were derivatized with the hydroxymethyl benzoic acid linker and used as supports for the solid phase Claisen rearrangement of a support bound phenyl allyl ether. Both the silica gel and mesoporous supports were heated at 225 °C for 3 h to effect the Claisen rearrangement. The results showed that, compared to the same reaction run homogeneously, the silica gel support achieved similar total product yields and ratios for two Claisen products. The mesoporous supports were found to selectively produce one of the Claisen products over the other. Analysis shows that the molecules bound to the mesoporous support are physically further separated from each other as compared to those bound to the silica gel support. A mechanism is presented which accounts for the selectivity of the mesoporous support in forming one Claisen product over the other. The Claisen product was further derivatized to the resulting phenyl ethyl ether through a solid phase Mitsunobu reaction on the mesoporous support. This revised version was published online in August 2006 with corrections to the Cover Date.     

Superconductivity and possible overdoping in Lu1−x Ca x Ba2Cu3O7−δ

Structural and superconducting properties of the system Lu_1−x Ca _x Ba₂ Cu₃O_7−δ, both in bulk as well as thin film form, have been investigated. Presence of large Ca-ions at the Lu-sites is responsible for phase stability (in 1–2–3 phase) in bulk. In argon annealed tetragonal samples (δ:1) superconductivity is reinstated as in these samples, presence of Ca-ions lead to the generation of holes in the Cu−O planes. In oxygen annealed bulk samples and thin films, there is a large depression ofT _c due to divalent Ca-ions present in concentrationx<0.2. Our data indicate that this depression ofT _c is likely due to overdoping effect.     

Growth characteristics of chloride‐based SiC epitaxial growth

In this study some aspects of the chloride‐based CVD growth process have been investigated by using both the approach to add HCl to the standard precursors and by using the single molecule precursor methyltrichlorosilane (MTS). The efficiency of the process for different precursors, the growth rate stability and the effect that the C/Si and Cl/Si ratios have on the growth are studied. It is found that MTS is the most efficient precursor and that the growth becomes carbon limited at C/Si < 1. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A novel wavelength dispersive device with a dispersive element based on staircase-like straight and parallel arrayed waveguides

We propose a new type of arrayed waveguide grating (AWG) multiplexer/demultiplexer based on modified group refractive index. This device is composed by an array of straight and parallel waveguides of equal length and each waveguide consist of two sections with different width. The length of the two sections are changed from a waveguide to the adjacent one following a linear dependence resulting in a wavelength dispersive waveguide array. An example of the device design for silicon-on-insulator (SOI) platform is provided and numerical simulations have been carried out for various arrayed waveguide parameters. We demonstrate that the group index modification can be used for tailoring device dispersion properties, and that it can also result in new dispersion characteristics predicted numerically not observed in conventional AWGs. Additional advantages are that the demultiplexer does not necessarily require bending waveguide sections as in a conventional AWG (de)multiplexers, and thus yields highly compact devices with potentially very low insertion loss. Channel spacing of 1 nm have been predicted for sub-micron waveguides sizes. In this paper it is also proposed a novel wavefront converter based on waveguide array lens-like element with waveguides broadened sections. Numerical results for different input/output geometries are analized.