On Raman optical activity sign-switching between the ground and excited states leading to an unusual resonance ROA induced chirality

Raman optical activity (ROA) spectra recorded for a chiral naphthalene diimide derivative (nBu-NDI–BINAM) dissolved in a series of solvents exhibit strong solute to solvent induced chirality with: (1) dominating bands of solvents, (2) nBu-NDI–BINAM resonance ROA (RROA) bands which are barely visible, (3) monosignate RROA Solvent spectra with an unexpected sign concordant with that of the ECD band of the resonant electronic state, (4) bisignate RROA bands for a few solvents, and (5) superposition of non-resonant and resonant ROA bands of the chiral solvents. The unusual ROA enhancement was explained in terms of resonance energy transfer with resonant Raman emission. The surprising RROA sign-switching was found to be due to specific conformational equilibria where one solute conformer dominates in the ground and the other in the first excited singlet state, and, the signs of the related ECD bands of these two conformers are opposite.

Unusual solute to solvent induced chirality in ROA comes from specific conformer equilibria in the ground and the excited states.     

A New Chemical Method to Desulfenylate Indol-3-yl Sulfides

Abstract

Desulfenylation of indol-3-yl sulfides liberates the most reactive position of the ring for further transformations. The usual procedure, utilizing Raney Nickel (P. G. Gassman, et. al., J. Am. Chem. SOC. 1974,96, 5495) offers a limited scope due to incompatibility of a number of functional groups towards the reducing agent. Based on our recent mechanistic studies of the acid-catalysed rearrangement of indol-3-yl sulfides to indol-2-yl sulfides (P. Hamel, et. al., Chem. Commun. 1989, 63; J. Org. Chem. 1992, 57, 2694), we have developed a novel, non-reductive desulfenylation method which permits easy access to 3-unsubstituted indoles bearing a wide array of substituents. Thus, 3-indolyl sulfides, readily obtained from appropriate phenylhydrazines (via Fischer indolization) or anilines (Gassman method, vide infra) are smoothly desulfenylated in good yields in trifluoroacetic acid in the presence of an appropriate nucleophilic trapping agent. Thiols proved to be very effective trapping agents and thiosalicylic acid (TSA) is a thiol of choice, being non-volatile and easily separable from reaction products.     

Reinstallation of the COMPASS-D tokamak in IPP ASCR

The COMPASS-D tokamak, originally operated by UKAEA at Culham, UK, will be reinstalled at the Institute of Plasma Physics (IPP) AS CR. The COMPASS device was designed as a flexible tokamak in the 1980s mainly to explore the MHD physics. Its operation (with D-shaped vessel) began at the Culham Laboratory of the Association EURATOM/ UKAEA in 1992.The COMPASS-D tokamak will have the following unique features after putting in operation on IPP Prague. It will be the smallest tokamak with a clear H-mode and ITER-relevant geometry. ITER-relevant plasma conditions will be achieved by installation of two neutral beam injection systems (2 × 300 kW), enabling co-and counter-injections. Redeployment of the existing LH system (400 kW) is also envisaged. A comprehensive set of diagnostics focused mainly on the edge plasma will be installed.The scientific programme proposed for the COMPASS-D tokamak installed in IPP Prague will benefit from these unique features of COMPASS-D and consist of two main scientific projects, both highly relevant to ITER-Edge plasma physics (H-mode studies) and Wave-plasma interaction studies.The COMPASS-D tokamak will offer an important research potential as a small, flexible and low-cost facility with ITER-relevant geometry.     

Model of convergent extension in animal morphogenesis

We argue that energy minimization can explain the pattern of cell movements in the morphogenetic process known as convergent extension provided that the cell-cell adhesive energy has a certain type of anisotropy, which we describe. This single simple property suffices to cause the cell elongation, cell alignment, and lengthening of a cellular array that characterize convergent extension. We show that the final aspect ratio of the array of cells depends on the anisotropy and is independent of the initial configuration and of the degree of cell elongation.     

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.     

Microwave Correlation Reflectometry for Tokamak CASTOR

A correlation reflectometer in 8-mm wavelength range has been constructed and installed on CASTOR tokamak. The reflectometer can operate on three fixed frequencies (29, 33, and 35 GHz). This is universal correlation sine-cosine reflectometer, which can work in poloidal or toroidal correlation regime and in ordinary mode (O-mode) and/or extraordinary mode (X-mode). A computational method of a direct evaluation of the phase fluctuations as well as absolute value of the phase from sine-cosine data has been developed. Using this method the relative plasma density fluctuations in the CASTOR core plasma has been determined in the range of few percent under assumption of parabolic density distribution.     

Fourier analysis of scratches generated on m‐GaN substrates during polishing

Generation of scratches on surface of m‐plane GaN substrates due to polishing was studied by atomic force microscopy (AFM). For epi‐ready substrates AFM images confirm a flat surface with the atomic step roughness while a lot of scratches are visible in AFM images for partially polished GaN substrates. The Fourier analysis of AFM images show that scratches propagate easier along {c‐plane} and {a‐plane} directions on m‐plane GaN surface. This observation is an evidence of anisotropy of mechanical properties of GaN crystals in the micro‐scale. This anisotropy is directly correlated with the symmetry and atomic arrangement of m‐plane GaN.