Solvatochromism in Binary Mixtures: First Report on a Solvation Free Energy Relationship between Solvent Exchange Equilibrium Constants and the Properties of the Medium

We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromic indicators, hereafter designated as ""probes"", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr,, respectively. These can be divided into three pairs, each includes two probes of similar pK(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12 protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda(max) (of the probe intramolecular charge transfer) were converted into empirical polarity scales, E(T)(probe) in kcal/mol, whose values were correlated with the effective mole fraction of water in the medium, chi w(effective). This correlation furnished three equilibrium constants for the exchange of solvents in the probe solvation shell; phi(W/S) (W substitutes S): phi(S-W/W) (S-W substitutes W), and phi(S-W/S) (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi = constant + a alpha(BM) + b beta(BM) + s(pi*(BM) + d delta) + p log P(BM), where a, b, s, and p are regression coefficients alpha(BM), beta(BM), and pi*(BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors. In all cases, three descriptors gave satisfactory correlations; use of four parameters gave only a marginal increase of the goodness of fit. For phi(W/S), the most important descriptor was found to be the lipophilicity of the medium; for phi(S-W/W) and phi(S-W/S), solvent basicity is either statistically relevant or is the most important descriptor. These responses are different from those of E(T)(probe) of many solvatochromic indicators in pure solvents, where the importance of solvent basicity is usually marginal, and can be neglected.

Thermo-solvatochromism of merocyanine polarity probes - What are the consequences of increasing probe lipophilicity through annelation?

The question raised in the title has been answered by comparing the solvatochromism of two series of polarity probes, the lipophilicities of which were increased either by increasing the length of an alkyl group (R) attached to a fixed pyridine-based structure or through annelation (i.e., by fusing benzene rings onto a central pyridine-based structure). The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-methylquinolinium-4-yl)ethenyl]-phenolate (MeQMBr(2)) and 2,6-dibromo-4-[(E)-2-(1-methyl-acridinium-4- yl) ethenyl)]phenolate (MeAMBr(2) The solvatochromic behavior of these probes, along with that of 2,6dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl]phenol-ate(MePMBr(2)) was analyzed in terms of increasing probe lipophilicity, through annelation. Values of the empirical solvent polarity scale [E(T)(MePMBr(2))] in kcalmol(-1) correlated linearly with ET(30), the corresponding values for the extensively employed probe 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB). On the other hand, the nonlinear correlations of ET(MeQMBr(2)) or ET(MeAMBr(2)) with E(T)(30) are described by second-order polynomials. Possible reasons for this behavior include: i) self-aggregation of the probe, ii) photoinduced cis/trans isomerization of the dye, and iii) probe structure- and solvent-dependent contributions of the quinonoid and zwitterionic limiting formulas to the ground and excited states of the probe. We show that mechanisms (i) and (ii) are not operative under the experimental conditions employed; experimental evidence (NMR) and theoretical calculations are presented to support the conjecture that the length of the central ethenylic bond in the dye increases in the order MeAMBr(2) > MeQMBr(2) > MePMBr(2), That is, the contribution of the zwitterionic limiting formula predominates for the latter probe, as is also the case for RB, this being the reason for the observed linear correlation between the ET(MePMBr2) and the ET(30) scales. The effect of increasing probe lipophilicity on solvatochromic behavior therefore depends on the strategy employed. Increasing the length of R affects solvatochromism much less than annelation, because the former structural change hardly perturbs the energy of the intramolecular charge-transfer transition responsible for solvatochromism. The thermo-solvatochromic behavior (effect of temperature on solvatochromism) of the three probes was studied in mixtures of water with propanol and/or with DMSO. The solvation model used explicitly considers the presence of three ""species"" in the system: bulk solution and probe solvation shell [namely, water (W), organic solvent (Solv)], and solvent-water hydrogen-bonded aggregate (Solv-W). For aqueous propanol, the probe is efficiently solvated by Solv-W; the strong interaction of DMSO with W drastically decreases the efficiency of Solv-W in solvating the probe, relative to its precursor solvents. Temperature increases resulted in desolvation of the probes, due to the concomitant reduction in the structured characters of the components of the binary mixtures.

Feasible estimation of generalized linear mixed models (GLMM) with weak dependency between groups

This paper presents a two-step pseudo likelihood estimation technique for generalized linear mixed models with the random effects being correlated between groups. The core idea is to deal with the intractable integrals in the likelihood function by multivariate Taylor's approximation. The accuracy of the estimation technique is assessed in a Monte-Carlo study. An application of it with a binary response variable is presented using a real data set on credit defaults from two Swedish banks. Thanks to the use of two-step estimation technique, the proposed algorithm outperforms conventional pseudo likelihood algorithms in terms of computational time.

Three principles of competitive nonlinear pricing

We make three contributions to the theory of contracting under asymmetric information. First, we establish a competitive analog to the revelation principIe which we call the implementation principIe. This principIe provides a complete characterization of all incentive compatible, indirect contracting mechanisms in terms of contract catalogs (or menus), and allows us to conclude that in competi tive contracting situations, firms in choosing their contracting strategies can restrict attention, without loss of generality, to contract catalogs. Second, we establish a competi tive taxation principIe. This principIe, a refinement of the implementation principIe, provides a complete characterization of all implementable nonlinear pricing schedules in terms of product-price catalogs and allows us to reduce any game played over nonlinear pricing schedules to a strategically equivalent game played over product-price catalogs. Third, using the competitive taxation principIe and a recent result due to Reny (1999) on the existence of Nash equilibria in discontinuous games, we demonstrate the existence of a N ash equilibrium for the mixed extension of the nonlinear pricing game.

Influence of the Substitutional Solute on the Mechanical Properties of Ti-Nb Binary Alloys for Biomedical Use

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optimised placement of control and protective devices in electric distribution systems through reactive tabu search algorithm

Optimised placement of control and protective devices in distribution networks allows for a better operation and improvement of the reliability indices of the system. Control devices (used to reconfigure the feeders) are placed in distribution networks to obtain an optimal operation strategy to facilitate power supply restoration in the case of a contingency. Protective devices (used to isolate faults) are placed in distribution systems to improve the reliability and continuity of the power supply, significantly reducing the impacts that a fault can have in terms of customer outages, and the time needed for fault location and system restoration. This paper presents a novel technique to optimally place both control and protective devices in the same optimisation process on radial distribution feeders. The problem is modelled through mixed integer non-linear programming (MINLP) with real and binary variables. The reactive tabu search algorithm (RTS) is proposed to solve this problem. Results and optimised strategies for placing control and protective devices considering a practical feeder are presented. (c) 2007 Elsevier B.V. All rights reserved.

Mixing, demixing, and structure formation in a binary dipolar Bose-Einstein condensate

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dependence of the nonlinear electrical behavior of SnO2-based varistors on Cr2O3 addition

Tin dioxide varistors doped with Coo, ZnO, Ta2O5 and Cr2O3 were prepared by the mixed oxide method. Temperature dependent impedance spectroscopy revealed two different activation energies, one at low frequencies and the other at high frequencies. These activation energies were associated with the adsorption and reaction of O-2 species at the grain boundary interface. We show that Cr2O3 improves the varistor properties, generating sites for the adsorption of O' and O at the grain boundary region. The O' and O defects are truly responsible for the barrier formation at the grain boundary interface. (c) 2005 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Mixed micelles of the anionic surfactant sodium dodecyl sulfate and the nonionic pentaethylene glycol mono-n-dodecyl ether in solution

Dynamic light scattering, surface tension, and clouding temperature have been monitored to elucidate the solution properties of mixed micelles formed between the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant pentaethylene glycol mono-n-dodecyl ether (C12E5) over a wide range of surfactant concentration and temperature. Addition of 0.1 M NaCl shifts the relaxational modes to higher frequency and lowers the clouding temperature (T-c) of the nonionic surfactant solution by about 1 degrees C compared to the salt-free system. T-c for the mixed surfactant solutions is higher than that of the binary C12E5 solutions and depends sensitively on the concentration of the two surfactants but increases only slightly when the total surfactant concentration is increased at a given molar C12E5/SDS concentration ratio. With C12E5/SDS = 5.7, for example, T-c is 46.0 and 47.5 degrees C, respectively, at 5 and 70 mM of C12E5 the mixed solutions are homogeneous and stable and contain nonspherical micelles, which are close to monodisperse over a range of surfactant concentrations and temperature. The mixed system has a lower Krafft point than binary SDS solutions and shows an approximately ideal behavior in contrast to the binary C12E5 solution. The hydrodynamic radius (RH) of the mixed micelle increases with temperature as do C12E5 micelles in the binary solutions and also with increasing C12E5/SDS ratio. At 25 degrees C, the critical micelle concentration of the mixed solution lies between those of the individual surfactants and decreases as the C12E5/SDS ratio is increased.

Efficient linear programming algorithm for the transmission network expansion planning problem

The transmission network planning problem is a non-linear integer mixed programming problem (NLIMP). Most of the algorithms used to solve this problem use a linear programming subroutine (LP) to solve LP problems resulting from planning algorithms. Sometimes the resolution of these LPs represents a major computational effort. The particularity of these LPs in the optimal solution is that only some inequality constraints are binding. This task transforms the LP into an equivalent problem with only one equality constraint (the power flow equation) and many inequality constraints, and uses a dual simplex algorithm and a relaxation strategy to solve the LPs. The optimisation process is started with only one equality constraint and, in each step, the most unfeasible constraint is added. The logic used is similar to a proposal for electric systems operation planning. The results show a higher performance of the algorithm when compared to primal simplex methods.

An implementation of modified scatter search algorithm to transmission expansion planning

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Spectrophotometric study of binary and ternary systems involving metal ions and benzylidenepyruvates: Equilibria in aqueous solutions

The protonation of 4-dimethylaminobenzylidenepyruvate (DMBP) and 2-chloro-4-dimethylaminobenzylidenepyruvate (2-CI-DMBP) and their complex formation with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Al(III) have been studied by potentiometric and spectrophotometric methods at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. The stability order found for 1 :1 complexes of both ligands is Al(III) > Cu(II) > Pb(II) > Ni(II) > Zn(II) > Co(II) > Cd(II) > Mn(II). The stability changes move in the same direction as the pKa of the ligands. The results are compared with literature values reported for metal ion pyruvate systems. Thermodynamic stabilities of ternary complexes formed in Cu(II)-B-L- systems, where B = 2,2′-bipyridyl (bipy), ethylenediamine or glycinate and L = DMBP or 2-CI-DMBP, were also determined. The Cu(bipy)L+ species are more stable than would be expected on purely statistical grounds. The importance of the :t system associated with bipy on the enhanced stability of its mixed ligand complexes is stressed. Analytical applications of the investigated ligands are outlined.

Optimal linear and nonlinear control design for chaotic systems

In this work, the linear and nonlinear feedback control techniques for chaotic systems were been considered. The optimal nonlinear control design problem has been resolved by using Dynamic Programming that reduced this problem to a solution of the Hamilton-Jacobi-Bellman equation. In present work the linear feedback control problem has been reformulated under optimal control theory viewpoint. The formulated Theorem expresses explicitly the form of minimized functional and gives the sufficient conditions that allow using the linear feedback control for nonlinear system. The numerical simulations for the Rössler system and the Duffing oscillator are provided to show the effectiveness of this method. Copyright © 2005 by ASME.

A nonlinear model for the long-term hydro-thermal generation scheduling problem over multiple areas with transmission constraints

This paper presents a nonlinear model with individual representation of plants for the centralized long-term hydrothermal scheduling problem over multiple areas. In addition to common aspects of long-term scheduling, this model takes transmission constraints into account. The ability to optimize hydropower exchange among multiple areas is important because it enables further minimization of complementary thermal generation costs. Also, by considering transmission constraints for long-term scheduling, a more precise coupling with shorter horizon schedules can be expected. This is an important characteristic from both operational and economic viewpoints. The proposed model is solved by a sequential quadratic programming approach in the form of a prototype system for different case studies. An analysis of the benefits provided by the model is also presented. ©2009 IEEE.

Distribution system restoration in a DG environment using a heuristic constructive multi-start algorithm

This paper proposes a heuristic constructive multi-start algorithm (HCMA) to distribution system restoration in real time considering distributed generators installed in the system. The problem is modeled as nonlinear mixed integer and considers the two main goals of the restoration of distribution networks: minimizing the number of consumers without power and the number of switching. The proposed algorithm is implemented in C++ programming language and tested using a large real-life distribution system. The results show that the proposed algorithm is able to provide a set of feasible and good quality solutions in a suitable time for the problem. © 2011 IEEE.