Isomer-specific fuel destruction pathways in rich flames of methyl acetate and ethyl formate and consequences for the combustion chemistry of esters

The influences of fuel-specific destruction pathways on flame chemistry are determined for two isomeric ester fuels, methyl acetate, CH3(CO)OCH3, and ethyl formate, H(CO)OC2H5, used as model representatives for biodiesel compounds, and their potential for forming air pollutants is addressed. Measurements are presented of major and intermediate species mole fractions in premixed, laminar flat flames using molecular-beam sampling and isomer-selective VUV-photoionization mass spectrometry. The observed intermediate species concentrations depend crucially on decomposition of the different radicals formed initially from the fuels. The methyl acetate structure leads to preferential formation of formaldehyde, while the ethyl formate isomer favors the production of acetaldehyde. Ethyl formate also yields higher concentrations of the C2 species (C2H2 and C2H4) and C4 species (C4H2 and C4H4). Benzene concentrations, while larger for ethyl formate, are at least an order of magnitude smaller for both flames than seen for simple hydrocarbon fuels (ethylene, ethane, propene, and propane).     

Confinement effects on product selectivity in the pyrolysis of phenethyl phenyl ether in mesoporous silica

Pyrolysis of phenethyl phenyl ether confined in mesoporous silicas by covalent grafting results in significantly increased product selectivity compared with fluid phases.     

The interaction of EDTA with barium sulfate

Ethylenediaminetetraacetic acid (EDTA) is a known complexing agent that interacts with a host of cations. In this paper, various techniques are used to elucidate the mechanism of interaction between EDTA and barium sulfate surfaces. It is shown that complexation with metal ions is not sufficient to explain the inhibition of barite crystallization but that other processes such as chemisorption must also occur. EDTA is shown to always adsorb as the mono-protonated species - suggesting that the molecule is able to lose a proton when it adsorbs at lower pH. Molecular modelling shows that the interaction of the surface barium ions with the carboxylate group is an important one. Finally, in situ turbidity measurements provide information about the mechanism of nucleation/growth modification. It is found that the EDTA molecule inhibits barium sulfate nucleation and that this could be its primary means of inhibiting precipitation of barium sulfate.     

Biocatalytic microcontact printing

Immobilized biocatalytic lithography is presented as an application of soft lithography. In traditional microcontact printing, diffusion limits resolution of pattern transfer. By using an immobilized catalyst, the lateral resolution of microcontact printing would depend only on the length and flexibility of the tether (<2 nm) as opposed to diffusion (>100 nm). In the work, exonuclease reversibly immobilized on a relief-patterned stamp is used to ablate ssDNA monolayers Percent of ablation was determined via confocal fluorescence microscopy to be approximately 70%.     

Mode detection in turbofan inlets from near field sensor arrays

Knowledge of the modal content of the sound field radiated from a turbofan inlet is important for source characterization and for helping to determine noise generation mechanisms in the engine. An inverse technique for determining the mode amplitudes at the duct outlet is proposed using pressure measurements made in the near field. The radiated sound pressure from a duct is modeled by directivity patterns of cut-on modes in the near field using a model based on the Kirchhoff approximation for flanged ducts with no flow. The resulting system of equations is ill posed and it is shown that the presence of modes with eigenvalues close to a cutoff frequency results in a poorly conditioned directivity matrix. An analysis of the conditioning of this directivity matrix is carried out to assess the inversion robustness and accuracy. A physical interpretation of the singular value decomposition is given and allows us to understand the issues of ill conditioning as well as the detection performance of the radiated sound field by a given sensor array.     

Multiscale Dewetting of Low‐Molecular‐Weight Block Copolymer Ultrathin Films

Ultrathin films of a low‐molecular‐weight block copolymer spontaneously dewet after several days at ambient temperature. Film rupture produces macroscopic holes and a residual pancake brush layer ≈ 2 nm thick with intermittent mounds measuring up to 25 nm in thickness. Multiscale dewetting likewise occurs when the films are heated and returned to ambient temperature. Regardless of the surface pattern that forms during heating, submicron mounds develop on the dewetted copolymer film, and fine holes emerge along the substrate surface, after cooling.     

Ab initio calculations and molecular mechanics (MM3) force field development for ammonium and protonated aliphatic amines

The geometries and vibrational frequencies of 11 training molecules containing the ammonium ion moiety were calculated at the MP2/6-31+G* level of theory. Various torsional energy profiles were also calculated using this basis set. From those ab initio calculations, a molecular mechanics (MM3) force field was developed using our Parameter Analysis and Refinement Toolkit System (PARTS). Using this set of parameters, the MM3 force field was found to well reproduce the molecular geometries and vibrational spectra for the all training molecules. CPU time was reduced from days to seconds. The availability of this new force field dramatically increases the feasibility of the computer-assisted drug design involving ammonium and protonated amino groups. © 1997 by John Wiley & Sons, Inc. J Comput Chem 18 : 1371–1391, 1997