Regioselective,Asymmetric Formal Hydroamination of Unactivated Internal Alkenes

We report the regioselective and enantioselective formal hydroamination of unsymmetrical internal alkenes catalyzed by a copper catalyst ligated by DTBM‐SEGPHOS. The regioselectivity of the reaction is controlled by the electronic effects of ether, ester, and sulfonamide groups in the homoallylic position. The observed selectivity underscores the influence of inductive effects of remote substituents on the selectivity of catalytic processes occurring at hydrocarbyl groups, and the method provides direct access to various 1,3‐aminoalcohol derivatives with high enantioselectivity.     

Do triboluminescence spectra really show a spectral shift relative to photoluminescence spectra?

There are many reports in the literature of a spectral difference between the triboluminescence (TL) spectrum and the solid-state photoluminescence (PL) spectrum of the same compound. Numerous reasons have been suggested for this difference including pressure-induced changes to Franck-Condon factors during the lifetime of the TL light emission; self-absorption of the TL emission and fracture-induced symmetry changes perturbing the local field of the TL emitting species. However, in a number of cases, the luminescent spectra were recorded on different equipment with different spectral responses, with the resolution of either luminescent spectrum rarely quoted. To avoid artificial spectral differences, care must be taken to account for the response of each equipment over the wavelength range studied, as well as any resolution difference. We have therefore measured the TL and solid-state PL spectra of sixteen TL compounds on the same spectrometer at an identical resolution. Furthermore, the solid-state photoluminescent lifetime has been determined for all samples and the implication that these values have for observing pressure-induced (Franck-Condon) luminescent spectral changes discussed. Finally, in all cases where a significant difference was observed between TL and PL spectra, either self-absorption of the TL emission or fracture-induced perturbations of the local field have been evoked to explain the difference.     

The Ã1B2-X̃1A1 two-photon fluorescence excitation spectrum of 1,3-difluorobenzene

The $\text{A}\text{?}{}^1\text{B}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ system of 1,3-difluorobenzene has been observed using the technique of two-photon fluorescence excitation obtained with a pulsed dye laser. Calibration was achieved by a combination of the neon optogalvanic spectrum and etalon fringes. In circular, compared to linear, polarization the bands divide into two groups, those which are B₂-A₁ and which retain their intensity with circular polarization, and those which are A₁-A₁ and lose about 60% of their intensity under the same conditions. These two kinds of bands also show characteristic rotational contours. All of the A₁-A₁ bands whose assignments are established obtain their intensity through vibronic interaction in which the vibration ν′₂₅ (ν′₁₄ in the Wilson numbering) mixes the $\text{A}\text{?}$ with, presumably, the $\text{X}\text{?}$ state. There is an important Fermi resonance between the 9¹ and 10¹11¹ levels. Parts of the one-photon absorption spectrum have been photographed to identify sequences associated with the 0₀⁰ band for comparison with those observed in the two-photon spectrum, and to search for bands involving odd quanta of b₂ vibrations, including ν′₂₅ (ν′₁₄); none was found.     

The influence of edge detection algorithms on the estimation of the fractal dimension of binary digital images

The boundary of a fractal object, represented in a two-dimensional space, is theoretically a line with an infinitely small width. In digital images this boundary or contour is limited to the pixel resolution of the image and the width of the line commonly depends on the edge detection algorithm used. The Minkowski dimension was evaluated by using three different edge detection algorithms (Sobel, Roberts, and Laplace operator). These three operators were investigated because they are very widely used and because their edge detection result is very distinct concerning the line width. Very common fractals (Sierpinski carpet and Koch islands) were investigated as well as the binary images from a cancer invasion assay taken with a confocal laser scanning microscope. The fractal dimension is directly proportional to the width of the contour line and the fact, that in practice very often the investigated objects are fractals only within a limited resolution range is considered too.     

Studies on pyridazine azide cyclisation reactions

Reaction of sodium azide with 4-methyl-3,5,6-tribromopyridazine results in the formation of 3,5,6-triazide intermediate which could cyclise to give two possible bicyclic products while ab initio calculations show that the formation of a tricyclic compound is extremely energetically unfavourable. However, experimentally, only one major product is isolated. The structure of this unstable product has been conclusively established by X-ray crystallography as 3,5-diazido-4-methyl[1,5-b]tetrazolopyridazine confirming theoretical predictions.