Suppressed beta-hydride elimination in palladium-catalyzed cascade cyclization-coupling reactions: an efficient synthesis of 3-arylmethylpyrrolidines

[formula: see text] A novel type of palladium-catalyzed cascade cyclization-coupling reaction that proceeds with suppressed beta-hydride elimination has been found. One of the N-sulfonyl oxygens is suggested to coordinatively stabilize an alkylpalladium intermediate, thus preventing the intermediate from the usual beta-elimination. This is the first sequential palladium-catalyzed coupling reaction where the Suzuki and Heck reactions can compete. The reaction provides an efficient synthetic route to 4-methylene-3-arylmethylpyrrolidines, which are not readily available by other routes.     

Universal occurrence of soot superaggregates with a fractal dimension of 2.6 in heavily sooting laminar diffusion flames

Using small-angle light scattering we show that a new phase of soot with size ca. 10 microm and a fractal dimension of D approximately equal to 2.6 exists in laminar diffusion flames for a wide range of heavily sooting fuels. This new phase appears to be a supramicrometer extension of the well-known submicrometer, D approximately equal to 1.8 phase of soot formed via diffusion-limited cluster aggregation (DLCA). The occurrence of this new soot phase correlates with an empirical sooting index for fuels. This supports a creation scenario in which these supramicrometer aggregates are created via a percolation of the submicrometer, D approximately equal to 1.8 aggregates.     

Activation analysis of mercury in biological samples

A method has been developed for the determination of trace quantities of mercury in biological samples, in which homogeneous irradiation was achieved by introducing a rotating irradiation disk facility in the reactor pool water, and possible loss of mercury during chemical processing was reduced by using a simple procedure. This procedure involved the destruction of the sample in a reflux system with conc. HNO₃ or fuming HNO₃+H₂O₂ and subsequent isolation of mercury by spontaneous deposition on Cu sieves from dilute HNO₃(0.5–1.5N). The possibility of using Au or Co as standards, instead of mercury which is easily volatile, was also evaluated.     

ABS blends with phenoxy: morphology,thermal, mechanical and rheological properties

Blends of ABS (acrylonitrile–butadiene–styrene) with phenoxy(poly(hydroxyether bisphenol A)) were prepared using a Branender single screw extruder. Scanning and transmission electron micrographs (SEM, TEM) showed a typical two-phase morphology; particle-in-matrix (90/10) (ABS/phenoxy by weight), 70/30, 10/90), island/sea (30/70) and co-continuous (50/50) morphologies. The glass transition temperature (T_g) of SAN was almost unchanged in the blends, while the T_g of phenoxy increased by about 5 °C in the blends. The synergistic effect of tensile modulus and strength was noted in ABS-rich blends, where a drastic drop of ductility was seen, and the results were interpreted in terms of rubber particle migration form SAN to phenoxy phase, which was visualized by TEM. Melt viscosity showed yield in ABS-rich blends, and generally followed the log additivity.     

A Magnesium-Selective Ionophore Containing Four Amide Carbonyl Ligands Derived from L-Tartaric Acid and Axial Furano Oxygen Binding Sites

Octahedrally converging hexadentate macrocyclic receptors 1 and 2, based on L-tartaric acid and furanmoieties, were synthesized andtheir complexation properties studied. In this paper,magnesium ion selectivitiesdetermined by ISE experiments, chiroptical changes observedby circular dichroism(CD) on complexation, and association constants measuredby NMR titration arediscussed.     

Preparation of holographic gratings of liquid crystals dispersed in polyurethane acrylates under controlled reaction conditions.

Transmission gratings of holographic polymer-dispersed liquid crystals (HPDLC) are prepared under controlled reaction conditions by adding various amounts of chain-transfer agent (CTA). The resulting films have a higher gel content with lower cross-link density, less dark reaction, less grating shrinkage with much smoother LC/polymer interfaces, smaller induction period, and fast saturation of diffraction efficiency, which shows a maximum of 95 % with 1 % CTA. An optimum LC content of 35 % is verified on the basis of morphology and reaction kinetics.     

Insights into the structure of cyclohexane from femtosecond degenerate four-wave mixing spectroscopy and ab initio calculations

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes.     

Studies on mass production of transformed Panax ginseng hairy roots in bioreactor

The growth properties of Panax ginseng hairy roots transformed by Agrobacterium rhizogenes were compared between flask and aerated column or stirred bioreactor. In flask cultures, sucrose, initially 30 g/L, was nearly exhausted after 45 d of culture. The pH of the medium dropped from 5.5 to 4.96 after 10 d, but afterward it gradually increased to 6.4. After 45 d, hairy roots grew about 16-folds. The growth rate of hairy roots in air-bubble column or stirred bioreactor cultures was 1.13 (1.11) to 1.23 (1.20) g fresh wt (dry wt)/(g of cells·d), respectively. For both bioreactors, growth was about three times as high as in the flask cultivation.     

Surface-enhanced Raman study of organic sulfides adsorbed on silver

The surface-enhanced Raman scatterings of dimethyl sulfide, diethyl sulfide and dimethyl disulfide have been investigated in silver sol. The dimethyl disulfide molecule decomposes on silver to the corresponding mercaptide implying facile cleavage of its S---S bond. The C---S bond in dialkyl monosulfide appears not to cleave on silver. For diethyl sulfide, the C₂ conformation seems to be favorable on silver than other conformations.