Fluorescent probes for detection of amphiphilic polymer hydrophobic microdomains: A comparative study between pyrene and molecular rotors

 Cationic amphiphilic polymers (e.g. polyvinylpyridinium bromides and polyvinylimidazo-lium bromides) adopt a compact coiled form in aqueous solutions. In the case of former polymers, the resulting hydrophobic microdomains are evidenced only by fluorescence spectroscopy if a molecular rotor (DMAC) is used as a fluorescent probe, while the behaviour of the latter can be studied in aqueous solution by using both types of fluorescent probes, i.e., pyrene and the molecular rotor. The purpose of the present investigation deals with a comparative study between the magnitude of the local viscosity and the polarity of the hydrophobic microdomains generated by poly(3-hexadecyl-1-vinylimidazolium bromide) in an aqueous medium using pyrene and DMAC as fluorescent probes. Moreover, the results are compared with the data obtained with micelles of conventional surfactants such as the homopolymer repetitive unit model and CTAB. Received: 3 June 1996 Accepted: 29 September 1996     

New amphiphilic polymers: Poly(N-alkylacrylamide-CO-vinylpyridinium)

A series of new amphiphilic polymers containing various amounts of N-methyl-4-vinylpyridinium units as hydrophilic part and N-dodecylacrylamide or N-decylacrylamide units as hydrophobic part have been prepared by quaternizing the cognate copolymers. Their behaviour in aqueous solutions has been studied by viscometry, as well as by fluorescence spectroscopy and tensiometry. Results are discussed in detail and a conformational model of the macromolecules at the interface (water/methylcyclohexane) is proposed in relation to the formation of microdomains in the aqueous media.     

Dynamical couplings of the predissociative n = 3 triplet gerade complex of H2

We have performed ab initio configuration interaction calculations for the states involved in the n = 3 triplet gerade complex of H₂. The corresponding radial and rotational couplings needed in collisional studies have been evaluated analytically. Their physical origin, dynamical implications and comparison with previous data are discussed in some detail.     

Energetic and structural characterization of 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl): experimental and computational studies

The gaseous standard molar enthalpies of formation of two 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl), at T = 298.15 K, were derived using the values for the enthalpies of formation of the compounds in the condensed phase, measured by static bomb combustion calorimetry, and for the enthalpies of sublimation, measured by Knudsen effusion, using a quartz crystal oscillator. The three dimensional structure of 2‐tert‐butoxycarbonyl‐3‐methylquinoxaline‐1,4‐dioxide has been obtained by X‐ray crystallography showing that the two N? O bond lengths in this compound are identical. The experimentally determined geometry in the crystal is similar to that obtained in the gas‐phase after computations performed at the B3LYP/6‐311 + G(2d,2p) level of theory. The experimental and computational results reported allow to extend the discussion about the influence of the molecular structure on the dissociation enthalpy of the N? O bonds for quinoxaline 1,4‐dioxide derivatives. As found previously, similar N? O bond lengths in quinoxaline‐1,4‐dioxide compounds are not linked with N? O bonds having the same strength. Copyright © 2007 John Wiley & Sons, Ltd.     

A new diversity induction mechanism for a multi-objective ant colony algorithm to solve a real-world time and space assembly line balancing problem

Time and space assembly line balancing considers realistic multi-objective versions of the classical assembly line balancing industrial problems. It involves the joint optimisation of conflicting criteria such as the cycle time, the number of stations, and/or the area of these stations. The different problems included in this area also inherit the precedence constraints and the cycle time limitations from assembly line balancing problems. The presence of these hard constraints and their multi-criteria nature make these problems very hard to solve. Multi-objective constructive metaheuristics (in particular, multi-objective ant colony optimisation) have demonstrated to be suitable approaches to solve time and space assembly line balancing problems. The aim of this contribution is to present a new mechanism to induce diversity in an existing multi-objective ant colony optimisation algorithm for the 1/3 variant of the time and space assembly line balancing problem. This variant is quite realistic in the automative industry as it involves the joint minimisation of the number and the area of the stations given a fixed cycle time limit. The performance of our proposal is validated considering ten real-like problem instances. Moreover, the diversity induction mechanism is also tested on a real-world instance from the Nissan plant in Barcelona (Spain).     

Image registration with iterated local search

This contribution is devoted to the application of iterated local search to image registration, a very complex, real-world problem in the field of image processing. To do so, we first re-define this parameter estimation problem as a combinatorial optimization problem, then analyze the use of image-specific information to guide the search in the form of an heuristic function, and finally propose its solution by iterated local search. Our algorithm is tested by comparing its performance to that of two different baseline algorithms: iterative closest point, a well-known, image registration technique, a hybrid algorithm including the latter technique within a simulated annealing approach, a multi-start local search procedure, that allows us to check the influence of the search scheme considered in the problem solving, and a real coded genetic algorithm. Four different problem instances are tackled in the experimental study, resulting from two images and two transformations applied on them. Three parameter settings are analyzed in our approach in order to check three heuristic information scenarios where the heuristic is not used at all, is partially used or almost completely guides the search process, as well as two different number of iterations in the algorithms outer-inner loops. This work was partially supported by the Spanish Ministerio de Ciencia y Tecnología under project TIC2003-00877 (including FEDER fundings) and under Network HEUR TIC2002-10866-E.     

Thermodynamic Investigation of the Micellization and the Adsorption of Short Perfluoroalkylated Diols via Fluorescence Spectroscopy and Tensiometry

The micellization and adsorption of two short chain perfluorodiols 3,3,4,4,5,5,6,6,6-nonafluorohexane-1,2-diol (nFHD) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1,2-diol (tFOD) are examined from a thermodynamic point of view as a function of temperature and methanol content. The microenvironment of the fluorinated aggregates is evaluated by the fluorescence probe method using pyrene and a molecular rotor 1,1-dicyano-4-p-dimethylaminophenyl)-1,3-butadiene (DMAPhC). The formation of micellar aggregates being evidenced, the results are discussed in terms of the polarity and of the cohesion behavior of the micellar aggregates by taking into account the methanol (MeOH) effect. The critical micellization concentrations thus determined are compared with those given by surface tension measurements. Micellar and adsorption thermodynamic parameters such as Gibbs free energies, enthalpies, and entropies are determined together with the surface areas. The results are compared with literature data and discussed. A model for describing the adsorption process of the fluorinated compounds upon the influence of methanol is finally proposed. Copyright 2001 Academic Press.     

GRASP and path relinking hybridizations for the point matching-based image registration problem

In the last decade, image registration has proven to be a very active research area when tackling computer vision problems, especially in medical applications. In general, image registration methods aim to find a transformation between two images taken under different conditions. Point matching is an image registration approach based on searching for the right pairing of points between the two images, which involves a combinatorial optimization problem. From this matching, the registration transformation can be inferred by means of numerical methods.