Flexibility transitions and looped adsorption of wormlike chains

When deposited from a solution onto a surface, superpolymeric chains display revealing transitions in their apparent stiffness. With simulated chains in adsorption, we varied the backbone rigidity and measured the chain persistence length (l_Pads). As the three‐dimensional persistence length (l_P3) increases toward the contour length, a transition can be seen from l_Pads = l_P2 (i.e., the two‐dimensional persistence length) to l_Pads = l_P3. Looped conformations decrease in frequency with a distinct nonlinear dependence. Finally, comparisons with experiments on polymeric worm micelles and purified neurofilaments demonstrate a simple new method for assessing the flexibility of these novel superpolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 280–286, 2005     

Linear free energy relationships in C-N bond dissociations in molecular ions of 4-substituted N-(2-furylmethyl)anilines in the gas phase

The substituent effect on the reactivity of the C-N bond of molecular ions of 4-substituted N-(2-furylmethyl)anilines toward two dissociation pathways was studied. With this aim, six of these compounds were analyzed by mass spectrometry using electron ionization with energies between 7.8 and 69.9 eV. Also, the UB3LYP/6-31G (d,p) and UHF/6-31G (d, p) levels of theory were used to calculate the critical energies (reaction enthalpies at 0 K) of the processes that lead to the complementary ions [C(5)H(5)O](+) and [M - C(5)H(5)O](+), assuming structures that result from the heterolytic and homolytic C-N bond cleavages of the molecular ions, respectively. A kinetic approach proposed in the 1960s was applied to the mass spectral data to obtain the relative rate coefficients for both dissociation channels from ratios of the peak intensities of these ions. Linear relationships were obtained between the logarithms of the relative rate coefficients and the calculated critical energies and other thermochemical properties, whose slopes showed to be conditioned by the energy provided to the compounds within the ion source. Moreover, it was found that the dissociation that leads to [C(5)H(5)O](+) is a process strongly dependent upon the electron withdrawing or donating properties of the substituent, favored by those factors that destabilize the molecular ion. On the contrary, the dissociation that leads to [M - C(5)H(5)O](+) is indifferent to the polar electronic effects of the substituent. The abundance of both products was governed by the rule of Stevenson-Audier, according to which the major ion is the one of less negative electronic affinity.     

Synthesis and characterization of (6‐{[2‐(pyridin‐2‐yl)hydrazinylidene]methyl}pyridin‐2‐yl)methanol: a supramolecular and topological study

Hydrazones exhibit a versatile chemistry and are of interest for their potential use as functional molecular systems capable of undergoing reversible changes of configuration, i.e. E/Z isomerization. The title compound, C₁₂H₁₂N₄O, has an E configuration with respect to the hydrazone C=N bond. The crystal packing is formed by N—H...N and O—H...N hydrogen bonds that give a two‐dimensional layer structure and C—H...C interactions associated with layer stacking to produce the three‐dimensional supramolecular structure. These intermolecular interactions were analyzed and quantified by the Hirshfeld surface method and the two‐dimensional supramolecular arrangement was topologically simplified as a hcb network.     

Relaxation Limit for Aw-Rascle System

We study the relaxation limit for the Aw-Rascle system of traffic flow. For this we apply the theory of invariant regions and the compensated compactness method to get global existence of Cauchy problem for a particular Aw-Rascle system with source, where the source is the relaxation term, and we show the convergence of this solutions to the equilibrium state.     

Americium separations from nitric acid process effluent streams

Plutonium recovery operations offer several points at which americium removal may be attempted, and we are evaluating two classes of materials targeted at different steps in the process. Extraction chromatography resin materials loaded with three different alkylcarbamoyl phosphinates and phosphine oxides are assessed for Am removal efficiency and Am/Fe selectivity from 1–7M nitric acid solutions. Commercial and experimental anion exchange resins are evaluated for total alpha-activity removal from post-evaporator solutions whose composition, relative to the original nitric acid effluent, is reduced in acid and greatly increased in total salt content. With both classes of materials, americium and/or total-alpha reduction is sufficient to meet regulatory requirements even under sub-optimal conditions. Batch distribution coefficients and column performance data are presented.     

Whitney preserving maps on finite graphs

For a Whitney preserving map f:X→G we show the following: (a) If X is arcwise connected and G is a graph which is not a simple closed curve, then f is a homeomorphism; (b) If X is locally connected and G is a simple closed curve, then X is homeomorphic to either the unit interval [0,1], or the unit circle S¹. As a consequence of these results, we characterize all Whitney preserving maps between finite graphs. We also show that every hereditarily weakly confluent Whitney preserving map between locally connected continua is a homeomorphism.     

Radiation synthesis of seroalbumin nanoparticles

Synthesis of small polymeric particles can be achieved by ionizing radiation technology via intramolecular crosslinking by gamma rays onto soluble polymer molecules in random coil conformation. Differently soluble globular proteins are naturally densely packed structures. Fragmentation and aggregation processes have been reported for irradiated globular proteins solutions with ionizing radiations.In this work we describe protein-based nanoparticles prepared by gamma irradiation of a soluble and globular protein, such as seroalbumin, as the basic building blocks keeping its original conformational shape. Protein nanoparticles in the range 20–40 nm were detected after gamma irradiation of the aqueous protein solution in the presence of polar organic solvents. Nanoparticles were characterized by DLS, fluorescence, and UV and CD spectroscopy, showing that the protein molecules keep their general three-dimensional structure into the created nanoparticle.