Modeling the chemistry of plasma polymerization using mass spectrometry

The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.     

Geometric H/D isotope effects and cooperativity of the hydrogen bonds in porphycene.

We investigate the primary, secondary, and vicinal hydrogen/deuterium (H/D) isotope effects on the geometry of the two intramolecular hydrogen bonds in porphycene. Multidimensional potential energy surfaces describing the anharmonic motion in the vicinity of the trans isomer are calculated for the different symmetric (HH/DD) and asymmetric (HD) isotopomers. From the solution of the nuclear Schr?dinger equation the ground-state wavefunction is obtained, which is further used to determine the quantum corrections to the classical equilibrium geometries of the hydrogen bonds and thus the geometric isotope effects. In particular, it is found that the hydrogen bonds are cooperative, that is, both expand simultaneously even in the case of an asymmetric isotopic substitution. The theoretical predictions compare favorably with NMR chemical-shift data.     

Microwave accelerated aza-Claisen rearrangements

The microwave-assisted thermal aza-Claisen rearrangement of allylic imidates and thiocyanates to the corresponding amides and isothiocyanates is investigated. Significant accelerations of the rearrangement of allylic imidates to amides and of allylic thiocyanates to isothiocyanates in comparison with standard thermal reactions is observed.     

Tandem asymmetric conjugate addition--silylation of enantiomerically enriched zinc enolates. Synthetic importance and mechanistic implications

[formula: see text] The zinc enolates, resulting from the copper-catalyzed enantioselective conjugate addition of dialkyl zinc reagents to cyclic and acyclic enones, could be trapped, quantitatively, as silyl enol ethers with TMSOTf in apolar solvents or with TMSCI and NEt3. These enantiomerically enriched silyl enol ethers were submitted to four synthetic transformations to show their synthetic utility. The zinc enolates obtained from acyclic enones were found to be configurationally stable, as shown by the stereochemistry of the silyl enol ethers.     

Rapid parallel synthesis of polymer-bound enones utilizing microwave-assisted solid-phase chemistry

A microwave-assisted parallel solid-phase synthesis of a collection of 21 polymer-bound enones has been developed. The two-step protocol involves initial high-speed acetoacetylation of polystyrene Wang resin with a selection of seven common beta-ketoesters. When microwave flash heating at 170 degreesC was employed, complete conversions were achieved within 1-10 min, a significant improvement over the conventional thermal method, which takes several hours for completion. Significant rate enhancements were also observed for the subsequent microwave-heated Knoevenagel condensations with a second set of 13 different aldehydes. Reaction times were reduced to 30-60 min at 125 degreesC in the microwave protocol compared to 1-2 days using conventional thermal conditions. Kinetic comparison studies indicate that the observed rate enhancements can be attributed to the rapid direct heating of the solvent (1,2-dichlorobenzene) by microwaves rather than to any specific microwave effect. All reactions have been carried out in commercially available parallel reactors with on-line temperature measurement, designed specifically for use in multimode microwave cavities.     

Adaptive Filtering Revisited

This paper shows that the adaptive filtering and forecasting techniques proposed by Makridakis and Wheelwright can be viewed as approximations to a more precise filtering method in which the Kalman filter is applied to a dynamic autoregressive model which is a special case of the models of Harrison and Stevens. The correct "learning" or "training factors" are shown to be data-dependent matrices rather than scalar constants.     

The ϕ 2 4 quantum field as a limit of Sine-Gordon fields

We exhibit the λ? ₂ ⁴ quantum field theory as the limit of Sine-Gordon fields as suggested by the identity $$\varphi ^4 /4! = \mathop {\lim }\limits_{\varepsilon \to 0} (\varepsilon ^{ - 4} \cos \varepsilon \varphi - \varepsilon ^{ - 4} + \tfrac{1}{2}\varepsilon ^{ - 2} \varphi ^2 ).$$ The proofs of finite volume stability for the two models, due to Nelson and Fröhlich respectively, are unrelated. We find a generalized stability argument that incorporates ideas from both of the simpler cases. The above limit, for the Schwinger functions, then proceeds uniformly in ?. As a by-product, let (?,dμ) be a Gaussian random field, ? _K (1≦κ<∞) a regularization of ?, andV a function satisfying:

1. V(? _K )≧?ak ^α
2. ∥V(?) ?V(? _K )∥ _p≦bp ^β k ^?γ, 2≦p < ∞

Thene ^?V(?)∈L ¹(dμ) provided α(β?1)<γ.     

The Robertson-Walker metric and the symmetries belong to the family of contracted Ricci collineations

It is shown that the general form of the Robertson-Walker cosmological metric admits symmetry properties that are members of the symmetry family of contracted Ricci collineations. A particular form for the conservation law generator given by _j [(–g)^1/2(T _i ^j –1/2 _i ^jT ) ⁱ ] = 0 following in consequence of these symmetries is obtained and interpreted.     

On the decay of correlations inSO(n)-symmetric ferromagnets

We prove that for low temperaturesT the spin-spin correlation function of the two-dimensional classicalSO(n)-symmetric Ising ferromagnet decays faster than |x|^–constT providedn2. We also discuss a nearest neighbor continuous spin model, with spins restricted to a finite interval, where we show that the spin-spin correlation function decays exponentially in any number of dimensions.Work supported in part by NSF, Grant PHY76-17191A Sloan Fellow     

RNAi: running interference for the cell

RNA interference or RNAi is a recently characterized mechanism of eukaryotic gene regulation in which a short sequence of double-stranded RNA (dsRNA) specifically down-regulates expression of the associated gene. Preliminary characterization of this phenomenon has revealed a set of inter-related cellular pathways which appear to represent both a response to foreign RNA and a mechanism of endogenous gene regulation. Introduction of dsRNA into cells by a variety of means, including transfection of synthetic RNA duplexes, triggers the RNAi response resulting in specific suppression of target gene expression. Recent efforts on a genome wide scale have involved application of RNAi as an important new tool in cell biology to elucidate gene function in living cells.