Investigation of catalytic activities by differential thermal analysis

A calorimetric method is proposed to evaluate the catalytic activity of a solid catalyst with respect to the exothermic oxidation of Volatile Organic Compounds (VOC).This method employs a differential thermal analyzer in which an inert reference and a catalytically active sample are both fluxed at a constant rate with a reactive gaseous mixture composed of an inert gas (N₂ 90% vol.), oxygen and VOC, the last typically 900 to 5000 ppm. While the temperature is varied according to a predefined cycle, the output signal due to the exothermic reaction on the catalyst is continuously recorded. The design of the test chamber, the amount of catalyst, the shape of the holders and finally the flow rate and composition of the gaseous mixture should be carefully selected in order to achieve reproducible results.     

Studies on the synthetic compatibility of aryloxime linkers in the solid-phase synthesis of 3-aminobenzisoxazoles

Further exploration of the scope of our solid-phase method for the synthesis of 3-aminobenzisoxazoles (using the Kaiser oxime resin 1) is described. The effects of base, leaving group, and solvent on the nucleophilic aromatic substitution based resin-loading reaction are discussed. Representative aryloxime intermediates were subjected to a variety of acidic conditions commonly used in protecting group removal to establish the acid stability profile of this linker. Regioselectivity was evaluated with various di- and trifluorobenzonitriles, which gave single benzisoxazole products after loading and cyclorelease reactions. Substituent effects observed in the course of the acid stability and regioselectivity studies suggest that the nitrile plays a critical role in the oxime hydrolysis mechanism. Finally, to establish the compatibility of the aryloxime linker with a variety of useful on-resin synthetic transformations, functionalized substrates were loaded onto resin 1, and carbon-nitrogen, carbon-oxygen, and carbon-carbon bond-forming reactions were successfully executed.     

Statistical flow-oscillator modeling of vortex-shedding

The very important engineering problem of modeling the fluid-structure interaction occurring during the shedding of vortices has defied, and will probably continue to defy, a closed form exact solution for the foreseeable future. Therefore, an attempt must be made to extract relevant information about the process in order to be able to have a basic understanding of it for the purpose of analysis. A useful method involves the flow-oscillator concepts of Hartlen and Currie [1] redefined here for stochastic processes. The fluid-structure system is assumed to be governed by the cross-coupled equations

$\text{x}\text{?}\text{(t)+2ξω}{}_{\mathrm{n}}\text{x}\text{?}\text{(t)+ω}{}^2{}_{\mathrm{n}}\text{=C}{}_{\mathrm{e}}\text{(t)pV}{}^2{}_0\text{(t)DL/2m (i)}$

$\text{C}\text{?}{}_{\mathrm{e}}\text{(t)+{α ? βC}{}^2{}_{\mathrm{e}}\text{(t)+γC}{}^4{}_{\mathrm{e}}\text{(t)}}\text{C}\text{?}{}_{\mathrm{e}}\text{(t)+ω}{}^2{}_0\text{C}{}_{\mathrm{e}}\text{(t)=b}\text{x}\text{?}\text{(t), (ii)}$

where these equations govern the structure and fluid oscillators, respectively. The fluid damping is non-linear. These equations are taken as stochastic differential equations because of the many unpredictable, random effects that determine the loading and response. The lift coefficient C_$\text{l}$(t) is assumed to be a zero mean, narrow band process and the velocity V₀, composed of a uniform, constant velocity current plus oscillating wave, a broad band process. The analysis is based on solving equation (i) for x(t) by using Duhamel's integral and substituting its derivative $\text{x}\text{?}\text{(t)}$ into equation (ii). This equation is then used to derive the Fokker-Planck equation for the process C_$\text{l}$(t). To obtain the Fokker-Planck equation, slowly varying variables are replaced by their long-time averages [2] and then the method of stochastic averaging is employed [3, 4]. The moment equation for the lift-oscillator process is derived from the Fokker-Planck equation and, as equation (ii) is non-linear, one finds the moment equation to be in terms of higher order moments. A truncation scheme [5] is used to derive the moment generating function. It is possible then to generate the first and second order statistics of the lift coefficient and the structure response in terms of the empirical parameters of fluid damping. This work was carried out in conjunction with an analysis of ocean wave-current forces with application to offshore fixed structures [6].     

Allenyl esters as quenching agents for ruthenium olefin metathesis catalysts

In the attempt to synthesize substituted allenyl esters through a metathesis coupling of unsubstituted allenyl esters and alkenes using a variety of ruthenium catalysts, it was discovered that allenyl esters themselves cleanly arrested the activity of the catalysts. Further studies suggests possible utility of allene esters as general quenching agents for metathesis reactions. To explore this idea, several representative olefin metathesis reactions, including ring closing, were successfully terminated by the addition of simple allenyl esters for more convenient purification.     

An experiment to test the reality of de Broglie waves

A second-order interferometric experiment in which de Broglie waves pass through a set of beamsplitters and progressively lose intensity, leading to a decrease in the visibility, is presented. On the contrary, since the intensity reduction is the same in the two overlapping waves, quantum mechanics predicts a constant visibility.     

Total synthesis of the proposed structures of the DNA methyl transferase inhibitors peyssonenynes, and structural revision of peyssonenyne B

The purported structures of the peyssonenynes A and B isolated from Peyssonnelia caulifera, and considered to be geometric isomers at the acetoxyenediyne moiety, have been synthesized. The E and Z geometries of the synthetic compounds were secured by the magnitude of the (3)J(H9-C7) values measured using the EXSIDE band-variant of the gradient HSQC pulse sequence and by the chemical shifts of C(6). Comparison of the NMR data of the synthetic and natural products revealed that only those of the Z isomers matched, which correspond to peyssonenyne A. Using HPLC analysis it was found that peyssonenyne B must correspond to the sn-2 positional isomer of the Z sn-1/3 counterpart. The four synthetic sn-1/3 diastereomers are roughly equipotent as DNMT1 inhibitors when evaluated on a radioactive methyl transfer enzymatic assay after immunoprecipitation from K562 human leukemia cells with anti-DNMT1 antibody.     

The 5v 3 bands of 18O enriched ozone: line positions of 16O16O18O, 16O18O16O, 16O18O18O and 18O16O18O

The four 5v ₃ bands of ¹⁸O enriched ozone have been observed and analysed for the first time. Two species (¹⁶O¹⁸O¹⁶O and ¹⁸O¹⁶O¹⁸O) belong to the C_2v symmetry group and two other (¹⁸O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O) to the C_s symmetry group. They have been recorded at a resolution of 0.008 cm^?1 with a pathlength of 32.16 m. Despite the very weak absorptions observed, almost 250 energy levels have been derived for each of the 4 species, with J ? 35 and K _a ? 13, and suitable sets of Hamiltonian parameters have been determined. For 3 species it has been necessary to account for the resonance between the (005) and (311) states to correctly reproduce the spectra observed. These resonances, anharmonic for C_2v, and hybrid (both anhar-monic and Coriolis) for C_s symmetry confirm the accidentally extremely strong coupling between the (005) and (311) states for ¹⁶O₃, due in that case to the very close distance between unperturbed energy levels. This work also confirms the excellent prediction of band centres of these four species derived from the recently determined isotopically invariant molecular potential function.     

Distribution of n-alkanes, polynuclear aromatic hydrocarbons and nitrated polynuclear aromatic hydrocarbons between the fine and coarse fractions of inhalable atmospheric particulates.

The distribution ratios of n-alkanes, polynuclear aromatic hydrocarbons (PAHs) and nitrated PAH components between fine and coarse fractions of soot has been investigated in downtown Rome through three field campaigns carried out at different times of the year. The preferential accumulation of almost all species investigated onto fine particles has been observed in all field experiments performed. Moreover, nitrated PAHs had varied distributions, according to the origin of their occurrence in the atmosphere; in fact, congeners of photochemical origin accumulated more in fine particles than those released by primary sources.