Homoconjugated ketones with extended unsaturation: Wavelength-selective,regioselective, diastereoselective,and enantiospecific photochemical transformations of methyl 7-oxospiro[5.5]undeca-1,3-and -2,4,-diene-2-carboxylate

The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed.     

Adsorption of poly(vinyl pyrrolidone) on silica. II. The fraction of bound segments, measured by a variety of techniques

The adsorption of the flexible, linear, and nonionic homopolymer poly(vinyl pyrrolidone) from water and from 1,4-dioxane onto pyrogenic silica was studied. Results are reported for the adsorbed amount as a function of adsorption time, molecular mass, and molecular mass distribution (polydispersity). It is found that the adsorption of fractionated samples can be qualitatively explained by the recent theory of Scheutjens and Fleer. However, the influence of the solvent type is larger than predicted by this theory, and an extension of the model to account for this influence is suggested. The polydispersity effects encountered in adsorption isotherms are satisfactorily accounted for by a theory published by Cohen Stuart, Scheutjens, and Fleer.     

Institutional results of the Argentine Graduate Programme in Radiochemistry

Summary The evolution of radiochemistry at the National Atomic Energy Commission (CNEA) in Argentina is analyzed. The antecedents of the establishment, in 1998, of the Master Programme in Radiochemistry, jointly organized by CNEA and the Buenos Aires Regional Faculty of the National Technological University are revised, and the structure of the Programme is described. On the basis of the thesis works, the initial trends are discussed. Finally, the institutional results of the Programme are described.     

Wetting at a polymer gel–vapor interface; a system not influenced by a long-range van der Waals contribution

The exterior of a cross-linked polymer gel resembles a polymer brush. Such gel including its brush can be swollen by a good solvent. The detachment of the solvent–vapor (L–V) interface from the brush is controlled by the adsorption of polymer segments onto this interface and is to a very good approximation not influenced by long-range van der Waals contributions. A wetting transition in this system coincided with the adsorption–desorption transition for chains onto such L–V interface and has various unusual features. There are several indications that in practice this system should feature a second-order wetting transition.     

Windmill polynomials over fields of characteristic two

Chambers andSmeets [3] have designed a windmill arrangement of linear feedback shift registers (LFSRs) to generate pn-sequences overGF(2) with high speed. When the windmill hasv vanes, the associated minimal feedback polynomial (having degreen, relatively prime tov) can be taken to have the shapef ₁(x ^v )+x ⁿ f ₂(x ^–v ), where the polynomialsf ₁ andf ₂ have degree [n/v]. Their numerical evidence, whenv is divisible by 4, suggests that, surprisingly, there areno such windmill polynomials which are irreducible ifn±3 (mod 8), while about twice as many irreducible and primitive windmill polynomials as they expected occur ifn±1 (mod 8). A discussion of this behaviour is presented here with proofs. The brief explanation is that the Galois group of the underlying generic windmill polynomial overGF (4) is equal to the alternating groupA _n .     

A reliable two-dimensional gel electrophoresis procedure for separating neural proteins

A facile two-dimensional gel electrophoresis procedure has been developed for the analysis of neural tissue proteins which eliminates the serious problems associated with protein insolubility at the point of sample application onto polymerized first-dimension isoelectric focusing gels. This was accomplished by combining the methods of two previously published procedures. Our procedure provides an alternative method to the complex gel systems often employed for less soluble proteins, and yields very reproducible, high resolution separations. This procedure, which is in routine use in our laboratories for the analysis of total proteins extracted from retina and brain, produces protein patterns that are easily compared using both visual and computer-assisted image analysis techniques. Presented here are the results of a set of experiments designed to identify proteins unique to retina. This procedure should be useful to investigators studying protein changes resulting from genetic mutation, development, drug treatment or disease, in neural tissue as well as in virtually all other tissues.     

The mechanism of photoinduced acylation of amines by N-acyl-5,7-dinitroindoline as determined by time-resolved infrared spectroscopy

[reaction: see text] The photochemistry of N-acyl-5,7-dinitroindoline (1) was studied in acetonitrile using nanosecond time-resolved infrared (TRIR) spectroscopy. Upon photolysis, two nearly but not completely overlapping sets of transient IR bands are observed that are assigned to two non-interconvertible conformers of mixed acetic nitronic anhydride 7. While syn-7 reverts rapidly to 1, anti-7 is long-lived and is able to acylate amines. Results of density functional theory calculations support conclusions based on experimental TRIR data.