Laccase-catalyzed carbon-carbon bond formation: oxidative dimerization of salicylic esters by air in aqueous solution

The laccase catalyzed oxidative dimerization of salicylic esters, a rare example of a laccase-catalyzed carbon-carbon bond formation, was studied. This reaction allows the use of air as stoichiometric oxidant and proceeds in aqueous solution. The preparative scope and the mechanism of the method, which provides a new and convenient access to functionalized biaryls under mild conditions, were investigated.     

Ion Chromatographic determination of trace anions and cations in high-purity water

An ion chromatographic measuring system for the off-line and on-line determination of some trace anions and cations in high-purity water is presented. The ng/L level of anions and cations in 20-130 mL high-purity water can be analyzed after preconcentration on ion exchange columns. The concentrated solutes are eluted by eluents from the trap column and separated using a Dionex analytical column. The quantification of each ion is achieved using the suppressor technique and conductivity detector. The influence of various parameters on the results is discussed. The detection limits of cations and anions are between 10 and 30 ng/L for chloride, bromide, nitrate, phosphate, sulphate, sodium, ammonium, potassium, magnesium and calcium ions.     

Action des bromures de perfluoroalkylmagnésiums sur les aldéhydes α,βéthyléniques

Perfluoroalkylmagnesium bromide, C_nF_2n+1MgBr (n = 2, 6, 8), reacts with α,β-unsaturated aldehydes to give allylic alcohols as the sole products. No attack on the β-carbon atom of the carbonyl was detected, even when the reaction was carried out in the presence of CuCl. Part of the Grignard reagent decomposes to trans-R_FCFCFBr and trans-R_FCFCFI. Neither a mechanism involving dissociation into R⁺_F MgX^- nor the formation of a carbene intermediate is capable of explaining the thermal decomposition of the Grignard reagent.     

Motion of foam films in diverging-converging channels

Existing theories of the motion of foam films in capillaries often assimilate the pressure drop over the foam films to the static capillary pressure obtained from the Young-Laplace equation. Hence, they ignore the contribution of dynamic effects associated with the rapid stretching and contraction of the foam films to the overall viscous dissipation. This paper reports an investigation of the motion of foam films in axisymmetric diverging-converging channels, taking into account surface viscosity and elasticity. First, a phenomenological theory for the motion of the foam films is developed using simple physical arguments. We show that the displacement of the film obeys a nonlinear second-order differential equation, which can be solved numerically for the (dimensionless) distance from the inlet and the pressure drop as a function of time. Experiments with foam film motion, conducted using glass diverging-converging channels (minimum radius = 3.00 +/- 0,01 mm, maximum diameter = 7,98 +/- 0,01 mm) and nitrogen foam stabilized with sodium dodecyl sulfate (SDS) in brine, are discussed. For a single film motion in the diverging channel, we find that (a) the static pressure drop is a concave-upward function of distance and decreases from 1.0 to about 0.3, whereas (b) the dynamic pressure drop is concave downward and increases from 1 to a maximum of 1.3 and then decreases to 0.7. In the converging channel both the static and dynamic pressure drops are concave-downward functions, but the dynamic pressure drop values are always higher than the static ones. For two films the motions were found to be rather sensitive to the initial arrangement in the channel. The experiments are found to be in excellent agreement with the theoretical predictions. These observations imply that the large flow resistance obtained during foam flow in granular porous media, where converging-diverging channels are abundant, is largely due to the surface elasticity and viscosity of the films.     

Synthesis of a model system for the preparation of phloroglucinol containing natural products

A model system for the synthesis of phloroglucinol containing natural products was synthesized. Key steps include a manganic acetate-mediated cyclization and the facile conversion of an alkene into a β-bromoenone.     

Synthesis of aromatic polythioamide-oxothioxoquinazolines from bis(1,3,4-thiadiazoline-5-thione) and aromatic bis-o-amino esters

Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344–394°C in air.     

Kinetics of the hydrogen abstraction *CH3 + alkane --> CH4 + alkyl reaction class: an application of the reaction class transition state theory

Kinetics of the hydrogen abstraction reaction (*)CH(3) + CH(4) --> CH(4) + (*)CH(3) is studied by a direct dynamics method. Thermal rate constants in the temperature range of 300-2500 K are evaluated by the canonical variational transition state theory (CVT) incorporating corrections from tunneling using the multidimensional semiclassical small-curvature tunneling (SCT) method and from the hindered rotations. These results are used in conjunction with the Reaction Class Transition State Theory/Linear Energy Relationship (RC-TST/LER) to predict thermal rate constants of any reaction in the hydrogen abstraction class of (*)CH(3) + alkanes. Our analyses indicate that less than 40% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER method while comparing to explicit rate calculations the differences are less than 100% or a factor of 2 on the average.     

Theoretical study on the structure and property relationship of the cationic conjugated polyelectrolytes

A theoretical study using density functional theory was performed to understand the structure/property relationship of the cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined.     

Chemical activation of carbon nanofibers and nanotubes

Method of thermodynamic simulation was used to calculate the equilibrium parameters of reactions of graphite with anhydrous LiOH, NaOH, and KOH and with the alkalis in the presence of water vapor. The change in the specific surface area and mass loss were used to analyze the interaction of carbon nanofibers and multilayer carbon nanotubes produced by catalytic pyrolysis of CH₄ with the alkalis.     

Domino "[3+3]-cyclization-homo-Michael" reactions of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes

The Lewis acid mediated domino "[3+3]-cyclization-homo-Michael" reaction of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes allows an efficient one-pot synthesis of functionalized salicylates containing a halogenated side chain. A great variety of substitution patterns could be realized by variation of the starting materials and of the Lewis acid. The mechanism of the domino process was studied.