Adsorbed monolayer of H-bonded water molecules with and without neutral polymer molecules: A statistical mechanical treatment accounting for local order

A statistical mechanical treatment of a monolayer consisting both of H-bonded solvent molecules adsorbed in an unspecified number of orientations and of polymeric molecules of a neutral solute is provided. The different size of solvent and solute molecules is accounted for using Flory—Huggins statistics, whereas local order within the monolayer is accounted for using the quasi-chemical approximation. The above treatment is applied to a hexagonal array of adsorbed water molecules oriented in such a way as to be in a condition to be singly or double H-bonded laterally in the monolayer; a further water orientation characterized by full alignment of the dipole moment in the direction away from the electrode and simulating chemisorbed water monomers is included in the molecular model treatment. An adsorption isotherm is derived upon generalizing the molecular model at hand so as to include the presence of polymeric neutral solute molecules adsorbed in a single orientation. The model accounts satisfactorily for a number of salient features of experimental capacity curves at metal—water interphases in the absence of adsorbed solute species, as well as for the adsorption behaviour of aliphatic compounds on mercury, provided that the doubly H-bonded water molecules are excluded from the molecular model. A justification for this exclusion, based on the existence of H-bonds between the first and second layer of water molecules, is provided.     

Fragmentations induced by ion-atom reactions

Fragmentation of electron-impact-generated organic molecular cations, submitted to low-energy collisions with hydrogen in a MS/MS/MS multiquadrupole mass spectrometer, was promoted or significantly increased in the presence of atomic hydrogen generated from a microwave discharge. Loss of hydrogen alpha to a heteroatom and bond cleavage alpha to a carbonyl group are the major H-induced fragmentation pathways.     

Metal‐ion complexes in the angiogenetic effect

The complex formation between two polysaccharides, hyaluronic acid (Hyal) and its sulphated derivative (HyalS), and two metal ions, Cu²⁺ and Zn²⁺ was investigated in aqueous solution by thermodynamic and spectroscopic techniques. A stoichiometry for the complex species in solution was obtained. The bioactivity of the metal‐polysaccharide complexes was then evaluated in terms of their influence on endothelial cell migration and adhesion. The biological response of the complex species was found to be dependent of both the polysaccharide (Hyal or HyalS) and the metal ion (Cu²⁺ or Zn²⁺).     

Chemistry and biology of glycosaminoglycans in blood coagulation

Glycosaminoglycans (GAGs) are widely distributed in animal tissues where they are usually associated with proteins. Six types are commonly recognized: heparin (Hep), heparan sulfate (HS), dermatan sulfate (DS), chondroitin sulfate (Ch-S), keratan sulfate (KS) and hyaluronic acid (Hyal). They are structurally related with a carbohydrate backbone consisting of alternating hexuronic acid (L-iduronic acid and/or D-glucuronic acid) or galactose units and hexosamine (D-glucosamine or D-galactosamine) residues. All GAGs, except Hyal, show sulfate groups along their chains. Certain sulfate glycoaminoglycans have the ability to interfere with blood coagulation, as demonstrated by the extensive clinical use of Hep as an anticoagulant agent. HS and DS show a good anticoagulant activity, although weaker than that of Hep. In contrast, Ch-S has a low ability to inhibit plasma serine proteases, and KS and Hyal are devoid of any effect on coagulation cascade. The interaction between blood coagulation serine proteases and GAGs can be found to have two principle mechanisms: the specific “lock and key” binding and the nonspecific cooperative electrostatic association. This different ability of GAGs to interact with coagulation cascade proteins depends on the molecular weight, the ratio of iduronic/glucoronic acid and the sulfation degree. Many attempts have been made to improve or induce anticoagulant activity of natural GAGs-by chemical modification. Increasing sulfation degree of DS and Ch-S is followed by their biological activity increasing. Hyal, which is devoid of any anticoagulant effect, acquires a good ability to inactivate plasma serine proteases, i.e. thrombin and Factor Xa, when it is sulfated. This ability increases by increasing the number of sulfate groups per disaccharide unit, although the mechanism of action is different from that of Hep, but seems to be independent of its molecular weight.     

Measurement of Young''s modulus of cementitious materials using an electro-optic holographic technique

The electro-optic holographic technique has already been used to determine Young's dynamic modulus in homogeneous materials based on the resonance frequency of the analysed samples. This paper shows a modification of the determination method of this frequency that speeds up this process thus obtaining Young's modulus. Based on the visualisation of real time fringes drawn by exciting the rods at the 1000–10,000 Hz range, the proposed method allows us to determine their resonance frequencies.

This procedure has been used in the analysis of non-homogeneous materials such as mortar and concrete. The results obtained by this method show good correlation with those determined by the conventional compression method established by Una Norma Española (UNE) regulations, but with a smaller variability as far as measurements are concerned. The variation coefficient is less than 1% with the optical method as opposed to 3% with the compression technique.     

A Generalization of Entanglement to Convex Operational Theories: Entanglement Relative to a Subspace of Observables

We define what it means for a state in a convex cone of states on a space of observables to be generalized-entangled relative to a subspace of the observables, in a general ordered linear spaces framework for operational theories. This extends the notion of ordinary entanglement in quantum information theory to a much more general framework. Some important special cases are described, in which the distinguished observables are subspaces of the observables of a quantum system, leading to results like the identification of generalized unentangled states with Lie-group-theoretic coherent states when the special observables form an irreducibly represented Lie algebra. Some open problems, including that of generalizing the semigroup of local operations with classical communication to the convex cones case, are discussed. PACS: 03.65.Ud.