Nanostructure of polysaccharide complexes

The interaction of gum arabic (GA) with chitosan (Ch) of different degree of deacetylation was studied by turbidity measurements, dynamic light scattering and atomic force microscopy. The structure of the complexes was found to be directly related to the charge density of chitosan molecules. Gum arabic and chitosan with a degree of deacetylation of 75% form soluble complexes with a loosely globular structure of about 250 nm, at weight ratios up to 1.2, if the concentrations are kept low (total biopolymer concentration up to 0.06%). If chitosan has a higher charge density (degree of deacetylation of 93%), colloidal particles are formed, independently of the polymer concentration or ratio. At low concentrations and GA/Ch ratios of 1 or 1.2, the particles have diameters of 200-250 nm. The formation of soluble complexes is attributed to a chitosan lower charge density and the presence of non-charged monomers, which prevent the efficient self-assembly of the macromolecules.     

On the mechanism of the aza-Morita-Baylis-Hillman reaction: ESI-MS interception of a unique new intermediate

Solutions of aza-Morita-Baylis-Hillman (aza-MBH) reactions were directly monitored by ESI(+)-MS(/MS) spectrometry to obtain information on their mechanism. A unique bis-sulfonamide intermediate was intercepted and characterized and, based on this novel species, a mechanism that rationalizes the uniqueness of aza-MBH reactions is proposed.     

Limit laws of entrance times for homeomorphisms of the circle

Given a homeomorphismf of the circle with irrational rotation number and a descending chain of renormalization intervalsj _n off, we consider for each interval the point process obtained by marking the times for the orbit of a point in the circle to enterJ _n. Assuming the point is randomly chosen by the unique invariant probability measure off, we obtain necessary and sufficient conditions which guarantee convergence in law of the corresponding point process and we describe all the limiting processes. These conditions are given in terms of the convergent subsequences of the orbit of the rotation number off under the Gauss transformation and under a certain realization of its natural extension. We also consider the case when the point is randomly chosen according to Lebesgue measure,f being a diffeomorphism which isC ¹-conjugate to a rotation, and we show that the same necessary and sufficient conditions guarantee convergence in this case.     

Measurement of plane wave acoustic fields in flow ducts

The response of a fluid loaded plate is derived as function of the incident pressure in the fluid. The results are compared with full scale measurements made in the aft peak tank on a ship. Propeller induced pressure and hull plate velocity were measured with flush-mounted hydrophones and accelerometers. It is found that for a typical aft body construction the boundaries of the plate elements can be assumed to be simply supported. The plate model agrees well with full scale measurements down to 40 Hz. Below this frequency global vibrations determine the response of the hull. Both theoretical and experimental results indicate that the field induced by the vibrating plate elements can be considerable. The response of a plate can be decreased if the width of the plate is decreased or the plate thickness increased.     

Straightforward three-component palladium-catalysed synthesis of pyridazin-3(2H)-one libraries

A simple and straightforward three-component methodology for the solution phase high-throughput synthesis of 2,5-disubstituted pyridazin-3(2H)-one libraries has been developed. The diversity at position 5 of the heterocycle is determined by the use of Suzuki, Sonogashira, Heck or Stille coupling.     

Asymptotic limit law for the close approach of two trajectories in expanding maps of the circle

Summary Given two pointsx, yS ¹ randomly chosen independently by a mixing absolutely continuous invariant measure of a piecewise expanding and smooth mapf of the circle, we consider for each >0 the point process obtained by recording the timesn>0 such that |f ⁿ (x)–f ⁿ (y)|. With the further assumption that the density of is bounded away from zero, we show that when tends to zero the above point process scaled by –1 converges in law to a marked Poisson point process with constant parameter measure. This parameter measure is given explicity by an average on the rate of expansion off.Partially supported by FAPESP grant number 90/3918-5     

Tree Oriented Pullback

Given two epimorphisms of algebras A ? B and C ? B, we consider the pullback R. We introduce a particular class of algebras, the tree oriented pullback, where there is a close relationship between the category of indecomposable modules of these algebras. This leads us to prove that if A and C are hereditary algebras, then R is a tilted algebra.     

Switching and enhanced bistability in an asymmetric nonlinear directional coupler with a metamaterial channel

We numerically simulate the propagation and switching of ultra-short pulses in a metamaterial nonlinear directional asymmetric coupler where one of the guides is a conventional medium with a positive refraction index having a decreasing Kerr nonlinearity. The second guide is based in a metamaterial. A complete study of the nonlinear dynamics of ultra-short pulses propagation and switching in this new nonlinear directional coupler, including the transmission characteristics, bistability, critical power, compression factor and extinction coefficients are presented and compared to those of a conventional coupler. We conclude that the conventional coupler has higher transmission efficiency and extinction rate when compared with the metamaterial coupler. However the metamaterial coupler presents bistability which opens the possibility of such device to be used in a large variety of optical switching, storage and logical gates. We show that the input power range leading to bistability can be optimized by controlling the profile of the nonlinear refraction index of the conventional channel.     

The Plasticity of the Carbohydrate Recognition Domain Dictates the Exquisite Mechanism of Binding of Human Macrophage Galactose-Type Lectin

The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy.