Sulfur containing stable unsubstituted heptacene analogs

Heptacene and higher polyacenes have been sought for their high degree of charge carrier mobility in thin film transistors. Such acenes are, however, extremely unstable in ambient conditions. Approaches to obtain stable heptacenes include introduction of suitable substituents, of heteroatoms, or both. Methods to synthesize stable linear and a nonlinear unsubstituted heptacene analogs are discussed. No changes in the UV-visible absorption spectra in solution over time for these materials indicate higher oxidative stability compared to analogous polyacenes.     

AES and XPS investigations of the surface layers of porous silicon with Fe,Co, and Ni embedded pores

A Composite material of porous silicon with pore embedded d-metals por-Si(Me) can be used for fabricating memory cells. Por-Si layers have been produced by electrochemical etching of n-type silicon (100) according to the conventional process. Fe, Co, and Ni galvanic deposition in por-Si has been performed using aqueous solutions of corresponding sulfate salts. The Auger profiles of the obtained por-Si(Fe), por-Si(Co), por-Si(Ni) nanocomposites have shown that its surface layers (up to 40 nm thick) contained about 10% Fe and no more than 1% Co and Ni. These facts confirm data that Co and Ni, unlike Fe, penetrate deep into the silicon pores. The value of the magnetic moment for the nanocrystalline Ni atom incorporated into the por-Si(Ni) has been estimated based on the dependence of the relative intensity of the maxima for the 3s multiplet splitting of the X-ray phase spectra on the number of uncoupled d-electrons in systems with 3d metals. The obtained value ∼2.4 μB exceeds the atomic magnetic moment in bulk metallic Ni.     

Capillarity driven instability of a soft solid

We report the observation of a Plateau instability in a thin filament of solid gel with a very small elastic modulus. A longitudinal undulation of the surface of the cylinder reduces its area thereby triggering capillary instability, but is counterbalanced by elastic forces following the deformation. This competition leads to a nontrivial instability threshold for a solid cylinder. The ratio of surface tension to elastic modulus defines a characteristic length scale. The onset of linear instability is when the radius of the cylinder is one-sixth of this length scale, in agreement with theory presented here.     

On Backus Average for Generally Anisotropic Layers

In this paper, following the Backus (in J. Geophys. Res. 67(11):4427–4440, 1962) approach, we examine expressions for elasticity parameters of a homogeneous generally anisotropic medium that is long-wave-equivalent to a stack of thin generally anisotropic layers. These expressions reduce to the results of Backus (1962) for the case of isotropic and transversely isotropic layers.In the over half-a-century since the publications of Backus (1962) there have been numerous publications applying and extending that formulation. However, neither George Backus nor the authors of the present paper are aware of further examinations of the mathematical underpinnings of the original formulation; hence this paper.We prove that—within the long-wave approximation—if the thin layers obey stability conditions, then so does the equivalent medium. We examine—within the Backus-average context—the approximation of the average of a product as the product of averages, which underlies the averaging process.In the presented examination we use the expression of Hooke’s law as a tensor equation; in other words, we use Kelvin’s—as opposed to Voigt’s—notation. In general, the tensorial notation allows us to conveniently examine effects due to rotations of coordinate systems.     

ROSE BENGAL AGGREGATION IN RATIONALLY SYNTHESIZED DIMERIC SYSTEMS

Abstract— Rose Bengal derivatives (I-VI) have been synthesized as part of a program to study the spectroscopy of model systems for Hpd dimer. The absorption and emission spectra as a function of solvent are diagnostic for the formation of aggregated conformers. Based on our spectroscopic results we conclude that these compounds exist in open conformation in ethanol and other organic solvents, and that they form intramolecular dimers in aqueous solution.     

Unimolecular heteroaromatic photoinitiators

We report herein the synthesis and use for polymerization of new photoinitiators based on benzo(b)thiophene.     

Photodecomposition of organic peroxides containing coumarin chromophore: spectroscopic studies

The photodecomposition of coumarin-3-t-Bu peroxyester (1) and coumarin-3-carbonyl-m-chlorobenzoylperoxide (2) has been studied using nanosecond and femtosecond spectroscopy to elucidate the nature of transient species involved. Excitation of the coumarin chromophore leads to its singlet excited-state decaying with the rate 9 x 10(9) s(-1) that results from a composite of emission, intersystem crossing, thermal relaxation, and -O-O- bond homolysis. Dissociation of the weak oxygen-oxygen bond proceeds from both triplet and singlet excited states. The nature of this combination of states is predissociative rather than dissociative as demonstrated by the relatively slow rates of oxygen-oxygen bond rupture. The decomposition of 1 and 2 leads to the formation of coumarin-3-carbonyloxyl radical (R1). The later was observed spectroscopically on the nanosecond time scale using both time-resolved FTIR and UV-vis transient techniques. R1 is consumed in two competitive processes: unimolecular decarboxylation and bi-molecular hydrogen atom transfer. The rates of these reactions are 4.3 x 10(5) s(-1) and 1 x 10(6) M(-1) s(-1) respectively. The transition state geometries and energies of decarboxylation of R1 have been determined using DFT calculations and are compared with values for the benzoyloxyl radical. The decarboxylation of R1 proceeds via a transition state in which the carboxyl group is almost perpendicular (dihedral angle 114 degrees) to the plane of the coumarin chromophore. The transition state of the benzoyloxyl radical, in contrast, is flat (0 degrees). The varied transition state energies of the radicals (13.6 kcal/mol for coumarin carboxyl radical vs 8 kcal/mol for benzoyloxyl radical) correlate with different decarboxylation rates of these two species.     

Synthesis of acyclic bis-vinyl pyrimidines: a general route to d4T via metathesis

Unsaturated acyclic pyrimidine analogues, 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}uracil, 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}thymine and 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}cytosine having two asymmetric carbon atoms have been prepared in good yield starting from uridine and 5-methyluridine. The bis-vinyl thymine derivative underwent ring closure metathesis to give d4T, thus providing a novel synthesis of this compound.     

Determination of the enantiomeric purity of nucleoside analogs related to d4T and acyclovir,new potential antiviral agents,using liquid chromatography on cellulose chiral stationary phases

We reported a method of determination of enantiomeric purity of the new potential antiviral agents by direct analytical HPLC. Those agents are nucleoside analogs, having one chiral center. They are synthesized as a single enantiomer (R or S) by an asymmetric pathway. The chiral stationary phases chosen are silica-based cellulose tris-3,5-dimethylphenylcarbamate (Chiralcel OD-H), or tris-methylbenzoate (Chiralcel OJ). Resolution was achieved using normal-phase chromatography with a mobile phase consisting of n-hexane-alcohol (ethanol or 2-propanol) in various percentages. Furthermore the effects of structural features on retention, selectivity and resolution, as well as on the elution order were thoroughly studied. Differences in the lipophilicity of the compounds were also examined.