Chemosensors for the marine toxin saxitoxin

Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed.     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Algebraic properties of grids of projective lines

In this paper we compute the generators, the Hilbert function, and the Hilbert polynomial of the projective closure of affine lines which are parallel to the coordinate axes and pass through a lattice of points. We also consider the Cohen-Macaulay and seminormality property of their homogeneous coordinate ring. These lines are said to form a grid.     

Stick-slip instability analysis

A theoretical investigation of friction-induced self-excited oscillations for systems with one degree of freedom is proposed. The friction force is assumed as an odd function of the relative sliding velocity with a jump discontinuity at a value of zero for the relative sliding velocity. The friction characteristic is approximated with a piecewise linear function, i.e. straight line segments with a suitable slope. For the generic system belonging to the class in question, the stick-slip instability region is located on a suitable dimensionless map.

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Sommario Viene proposta un'indagine teorica sulle oscillazioni autoeccitate indotte dall'attrito per sistemi ad un grado di libertà. La forza d'attrito viene assunta come funzione dispari della velocità relativa tra le superfici accoppiate, con una discontinuità di prima specie in corrispondenza del valore nullo della velocità. La caratteristica d'attrito viene approssimata mediante una funzione lineare a tratti con segmenti di opportuna pendenza. Per il generico sistema appartenente alla classe in esame, si perviene all'individuazione, su opportuna mappa adimensionale, della regione di instabilità da stick-slip.