Influence of molecular architecture on the dewetting of thin polystyrene films

The control of dewetting for thin polymer films is a technical challenge and of significant academic interest. We have used polystyrene nanoparticles to inhibit dewetting of high molecular weight, linear polystyrene, demonstrating that molecular architecture has a unique effect on surface properties. Neutron reflectivity measurements were used to demonstrate that the nanoparticles were uniformly distributed in the thin (ca. 40 nm) film prior to high temperature annealing, yet after annealing, they were found to separate to the solid substrate, a silanized silicon wafer. Dewetting was eliminated when the nanoparticles separated to form a monolayer or above while below this surface coverage the dewetting dynamics was severely retarded. Blending linear polystyrene of similar molecular weight to the polystyrene nanoparticle with the high molecular weight polystyrene did not eliminate dewetting.     

Solid-phase synthesis of N-alkyl-N-(beta-keto)amides and 1,2,4,5-tetrasubstituted imidazoles using a traceless cleavage strategy

[reaction: see text] The solid-phase synthesis of N-alkyl-beta-keto)amides and 1,2,4,5-tetrasubstituted imidazoles was demonstrated using a traceless cleavage strategy based on benzylic acylammonium chloride reactivity. The approach enables the assembly of diverse compounds in a minimal number of steps in moderate to excellent yield (23-88%) and high purity (64-100%).     

Site-specific cleavage of human telomerase RNA using PNA-neocuproine.Zn(II) derivatives

Here we report the synthesis of a novel PNA based neocuproine.Zn RNA cleaving agent; we demonstrate that such agents sequence specifically cleave a synthetic RNA target and in particular the RNA component of human telomerase.     

On the claisen rearrangement of 1,4-diaryloxy-2-butynes

A proton nmr follow-up provided conclusive evidence for the involvement of two sequential Claisen rearrangements in the thermal rearrangement of 1,4-diaryloxy-2-butynes $\text{1}$to 11a-methylpterocarpans $\text{3}$. A detailed study of the rearrangement of 1,4-diaryloxy-2-butynes $\text{1}$ in polyethyleneglycol-200 (PEG-200), indicated a definite possibility of selective synthesis of either benzofuron (3,2-b )benzofuran $\text{4}$ or benzofuro(2,3-b)benzofuran $\text{5}$ by varying the temperature of the reaction alone     

The effect of the simultaneous variation of sample mass and heating rate in DTA and DSC

Quantitative correlations between kinetic parameters (energy of activation, E), procedural factors (sample mass, m, and heating rate, φ) and the dependent variables (the temperature of inception of reaction, T_i, and temperature T_α at which a constant fraction α has decomposed) have been derived for differential thermal analysis (DTA) and differential scanning calorimetry (DSC). The relations have the same form as those derived from earlier TG studies. The dependent variables T_i and T_α are related to m, φ and E by the equations

where C₃ and C₂ are constants, and

where C₄ and C₅ are constants for a given α. The variation of C₅ with α is given by C₅ = a + b α where a and b are constants. The equations are applicable to TG, DTA and DSC.     

Calculating intensities using effective Hamiltonians in terms of Coriolis-adapted normal modes

The calculation of rovibrational transition energies and intensities is often hampered by the fact that vibrational states are strongly coupled by Coriolis terms. Because it invalidates the use of perturbation theory for the purpose of decoupling these states, the coupling makes it difficult to analyze spectra and to extract information from them. One either ignores the problem and hopes that the effect of the coupling is minimal or one is forced to diagonalize effective rovibrational matrices (rather than diagonalizing effective rotational matrices). In this paper we apply a procedure, based on a quantum mechanical canonical transformation for deriving decoupled effective rotational Hamiltonians. In previous papers we have used this technique to compute energy levels. In this paper we show that it can also be applied to determine intensities. The ideas are applied to the ethylene molecule.     

Computer generation of edge groups and edge colorings of graphs

A computer code and nonnumerical algorithm are developed to construct the edge group of a graph and to enumerate the edge colorings of graphs of chemical interest. The edge colorings of graphs have many applications in nuclear magnetic resonance (NMR), multiple quantum NMR, enumeration of structural isomers of unsaturated organic compounds, and in the construction of configurational integral expansion series in statistical mechanics. The code developed is applied to many NMR graphs, complete graphs containing up to 10 vertices, and the Petersen graph.     

Synthesis of aminoquinolone derivatives

The synthesis of 3-amino-7-chloro-1-ethyl-6-fluoro-4(1H)quinolinone derivatives is described. These were investigated for their antibacterial activity.     

Spectrophotometric determination of the stability constants of HgCl(-)3 and HgCl(2-)4 in aqueous ethanol

The stability constants of HgCl(-)(3) and HgCl(2-)(4) in 60% aqueous ethanol (v/v) were determined by spectroscopy at 25 degrees and constant ionic strength and acidity; beta(1) was 3 +/- 1 and beta(2) 9 +/-3.     

Synthesis of homoceramides, novel ceramide analogues, and their lack of effect on the growth of hippocampal neurons

The synthesis of a new series of D-erythro-homoceramide analogues is described. Several synthetic approaches were investigated. Homoceramides can be successfully synthesized from L-homoserine as chiral building block and a protected Weinreb-amide as a key intermediate. The synthesis of short-chain analogues with a heptyl side chain, as well as with a phenyl residue in the sphingoid part (instead of the naturally occurring tridecyl side chain), was effected. The homoceramides 15-17 and 24 were investigated for their potential to reverse the inhibitory effect of fumonisin B(1) on axonal growth. Unfortunately, none of the tested compounds showed any biological activity due to their lack of metabolism to glucosylhomoceramide.