Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C−O Bond Formation

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.     

A search technique for global optimization in a chaotic environment

We describe a new algorithm which uses the trajectories of a discrete dynamical system to sample the domain of an unconstrained objective function in search of global minima. The algorithm is unusually adept at avoiding nonoptimal local minima and successfully converging to a global minimum. Trajectories generated by the algorithm for objective functions with many local minima exhibit chaotic behavior, in the sense that they are extremely sensitive to changes in initial conditions and system parameters. In this context, chaos seems to have a beneficial effect: failure to converge to a global minimum from a given initial point can often be rectified by making arbitrarily small changes in the system parameters.     

Pulsed laser deposition of nanostructured Ag films

Ultra-thin (0.5-5 nm) films of Ag have been prepared by pulsed laser deposition in vacuum using a 26 ns KrF excimer laser at 1 J cm⁻². The deposition was controlled using a Langmuir ion probe and a quartz crystal thickness monitor. Transmission electron microscopy showed that the films are not continuous, but are structured on nanometer size scales. Optical absorption spectra showed the expected surface plasmon resonance feature, which shifted to longer wavelength and increased in strength as the equivalent film thickness was increased. It is shown that Maxwell Garnett effective medium theory can be used to calculate the main features of optical absorption spectra.     

Expression ofAscaris suum malic enzyme in a mutantEscherichia coli allows production of succinic acid from glucose

Applied Biochemistry and Biotechnology - The malic enzyme gene ofAscaris suum was cloned into the vector pTRC99a in two forms encoding alternative arnino-termini. The resulting plasmids, pMEAl and...     

Recombination reactions of oxygen atoms on an anodized aluminum plasma reactor wall, studied by a spinning wall method

We have studied the recombination of O atoms on an anodized Al surface in an oxygen plasma, using a new "spinning wall" technique. With this method, a cylindrical section of the wall of the plasma reactor is rotated and the surface is periodically exposed to an oxygen plasma and then to a differentially pumped mass spectrometer (MS). By varying the substrate rotation frequency (r), we vary the reaction time (t(r)), that is, the time between exposure of the surface to O atoms in the plasma and MS detection of desorbing O(2) (t(r) = 1/2r). As t(r) is increased from 0.7 to 40 ms, the O(2) desorption signal decreases by a factor of 2 for an O-atom flux of 1 x 10(16) cm(-2) s(-1) and by a factor of 6 when the O flux is 1 x 10(17) cm(-2) s(-1). The O(2) signal decay is highly nonexponential, slowing at longer times and reaching zero signal as r --> 0. A model of O-atom recombination is compared with these time-dependent results. The model assumes adsorption occurs at surface sites with a range of binding energies. O can detach from these sites, become mobile, and diffuse along the surface. This leads to desorption of O, reattachment at free adsorption sites, and recombination to form O(2) that promptly desorbs. With several adjustable parameters, the model reproduces the observed shapes of the O(2) desorption decay curves and the lack of detectable desorption of O and predicts a high O-atom recombination coefficient on anodized aluminum.     

Determination of volatile organics in drinking water with USEPA method 524.2 and the ion trap detector

New drinking water regulations require the monitoring of eight volatile organic compounds that have established maximum contaminant levels (MCLs) and 51 other volatile organics for which MCLs are not established. A laboratory analytical method (Method 524.2) for the determination of 58 of these compounds is investigated, and precision and accuracy data are obtained. The method uses a standard inert gas purge extraction, isolation of the volatile organics on a three-stage solid-phase trap, thermal desorption into a gas chromatograph, separation with a fused-silica capillary column, and identification and measurement with a relatively low cost, benchtop ion trap detector that functions as a mass spectrometer. At a concentration of 2 micrograms/L (2 parts per billion), the grand mean measurement accuracy for 54 compounds was 95% of the true value with a mean relative standard deviation (RSD) of 4%. At 0.2 micrograms/L (200 parts per trillion), the grand mean measurement accuracy for 52 compounds was 95% of the true value with a mean RSD of 3%.     

Reactions of ortho oxy-substituted benzyl and phenacyl bromides in dimethyl sulphoxide

o-Acetoxy- and o-benzoyloxy-benzyl bromides and tosylates oxidatively rearrange in moist dimethyl sulphoxide to o-hydroxybenzyl esters; o-acetoxy- and o-benzoyloxy- phenacyl bromides rearrange to mixtures of 2-hydroxycoumaran-3-ones and o-hydroxyphenacyl esters; o-hydroxyphenacyl bromides also yield 2-hydroxycoumaran-3-ones, together with o-hydroxyphenacyl alcohols. 2-Acetoxybenzaldehyde is reductively rearranged by sodium borohydride to o-hydroxybenzyl acetate.     

α-Halogenoketones—XIV: Studies in the chemistry of 2''-hydroxyacrylophenones

The chromone epoxide ring system has been synthesised. Base-catalysed cyclization and dehydrobromination of α-bromo-o-acyl (aroyl) oxyacetopheones or 2-bromo-1, 3-diones yielded 3-substituted chromone epoxides. Acid-catalysed rearrangement of a 2-methylchromone epoxide in an aprotic solvent gave a 2-methylenech-romanonol, while a 3-methoxymethylchromone epoxide fragmented to chromonol under these conditions; in alchols, chromone epoxides gave 2-alkoxychromanonols.