GaCl(3)-catalyzed ortho-ethynylation of phenols

Phenols are ethynylated at the ortho position with silylated chloroethyne in the presence of a catalytic amount of GaCl3 and lithium phenoxide. The lithium salt is essential for the catalysis, and addition of 2,6-di(tert-butyl)-4-methylpyridine inhibits desilylation and hydration of the products. The reaction can be applied to various substituted phenols giving the ortho-ethynylated products in high yields, and the turnover numbers based on GaCl3 are between 8 and 10. The reaction mechanism involves addition of in situ formed phenoxygallium to the haloethyne followed by the elimination of GaCl3.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Selective foam separation of binary protein solution by SDS complexation method

A fundamental study about the selective foam separation of protein mixture was carried out. A solution containing two proteins, ovalbumin (OA) and lysozyme (LZ), and an anionic surfactant, sodium dodecyl sulfate (SDS), was adjusted to pH 6.0, which referred to an intermediate state between the isoelectric points of the proteins. The solution was processed by continuous foam separation. The results showed that a proper addition of SDS greatly improved the selective recovery of LZ to OA. The experimental data were well explained by a simple model that most of cationic protein molecules (LZ) are associated with SDS and the adsorption of all the species including LZ-SDS complexes are subjected to Langmuir adsorption isotherm. The results also showed that one of the Langmuir parameters, which means a kind of lyophillic property of adsorbed material, of LZ-SDS complexes was extremely large as compared with that of primary protein.     

A new synthesis of δ-lactones from oxetanes

Oxetanes were reacted with lithium enolates generated from esters or amides in the presence of boron trifluoride etherate to give δ-hydroxyesters or amides in high yield, which were hydrolyzed and converted to δ-lactones.     

Alignment of atomic autoionizing states created by slow Na++He collisions

Ejected-electron spectra have been measured for collisions of He-atoms with Na⁺-ions, whose impact energy ranged from 1.7 to 7.0 keV. The ion impact-energy dependence of the angular-differential cross-section of the ejected electrons has been investigated for an aligned autoionizing state Na**(2p ⁵ 3s ^{2 2} P), which has been created by charge transfer from the He-atoms. The alignment of the autoionizing state Na**(2p ⁵ 3s ^{2 2} P) is discussed in relation to the scattering angles of the Na⁺-ions. A complete longitudinal alignment has been observed with respect to the quasimolecular axis.     

Sparsely substituted chlorins as core constructs in chlorophyll analogue chemistry. I. Synthesis

Five routes to stable chlorins bearing 0 or 1 meso substituents have been investigated, among which reaction of a 9-bromo-1-formyldipyrromethane and 2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin proved most effective. Application of this route afforded metallochlorins [Cu(II), Zn(II), and Pd(II)] including the chlorin lacking any β-pyrrole and meso substituents.     

Quantitative analysis of photoelectron angular distribution of single-domain organic monolayer film: NTCDA on GeS(0 0 1)

Angle-resolved photoelectron spectra were measured for a single-domain monolayer film of naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) prepared on a cleaved GeS(0 0 1) surface using synchrotron radiation. The observed photoelectron angular distributions were analyzed by a calculation using the single-scattering approximation combined with molecular orbital calculation. With the help of the low-energy electron diffraction pattern, the structure of the NTCDA monolayer on GeS(0 0 1) was estimated quantitatively.