Thin films of carbohydrate based surfactants and carboxymethylcellulose acetate butyrate mixtures: Morphology and thermal behavior

Thin films of mixtures containing carboxymethylcellulose acetate butyrate (CMCAB) and carbohydrate based surfactant, namely, sorbitan monopalmitate (Span 40) or poly(oxyethylene) sorbitan monopalmitate (Tween 40) were spin-coated onto silicon wafers. The effect of surfactant concentration on resulting film morphology and surface toughness Was Studied by atomic force microscopy (AFM). Upon increasing the concentration of Span 40 in the mixture, films became rougher and more heterogeneous, indicating surface enrichment by Span 40 molecules. In the case of mixtures composed by CMCAB and Tween 40, the increase of Tween 40 in the mixture led to smoother and more homogeneous films, indicating compatibility between both components. Differential scanning calorimetry (DSC) revealed that Span 40 and Tween 40 act as plasticizers for CMCAB, leading to dramatic reduction of glass transition temperature of CMCAB, namely, Delta T(g) = -158 degrees C and Delta T(g)=-179 degrees C. respectively. (C) 2008 Elsevier B.V. All rights reserved.

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.

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co-Solvent Mixtures

Co-solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non-polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co-solvents in cellulose chemistry could be advanced: Appropriate co-solvents should have EN T values (normalized empirical polarity) > 0.3, very low ``acidity`` (alpha < 0.5), and relatively high ""basicity`` (beta >= 0.4). Moreover, novel promising co-solvents and binary co-solvent mixtures were identified.

Asymmetric phase-transfer catalytic sulfanylation of some 2-methylsulfinyl cyclanones. Modeling of the stereochemical course of the aldol reaction of (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone

Increased diastereoisomeric excesses are obtained for the sulfanylation reactions of some 2-methylsulfinyl cyclanones under phase-transfer catalysis using the chiral catalyst QUIBEC instead of TEBA. The optically pure (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone thus prepared reacts with ethyl acetate lithium enolate affording, after hydrolysis, (R)-2-[(ethoxycarbonyl)methyl]-2-hydroxycyclohexanone in 60% ee. Density functional theory calculations (at the B3LYP/6-311++G(d,p) level) can successfully explain the origin of this result as the kinetically favored axial attack of the nucleophile to the carbonyl group of the most stable conformer of the cyclanone, in which the CH(3)SO and CH(3)S groups are at the equatorial and axial positions, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Studies on chemo- and diastereo-selectivity of the Diels-Alder reactions of sulfinyltoluquinones with cyclopentadiene

Sulfinyltoluquinones (2a-2c) were submitted to thermal or catalyzed [4+2] cycloaddition reactions with cyclopentadiene. For p-tolylsulfinyltoluquinones (2b) and (2c), almost complete C2-C3-chemo- and unlike-diastereoselectivity was achieved by catalysis with ZnBr(2), yielding adducts 6. Under thermal conditions, Diels-Alder reaction took place at the C5-C6 double bonds of quinones 2a-2c, generating mixtures of diastereoisomeric like- and unlike-adducts 4.

Aromatic nitro substitution reaction between 4-nitro-N-n-butyl-1,8-naphthalimide and n-heptanethiol in water-methanol binary mixtures

The second-order rate constants of thiolysis by n-heptanethiol on 4-nitro-N-n-butyl-1,8-naphthalimide (4NBN) are strongly affected by the water-methanol binary mixture composition reaching its maximum at around 50% mole fraction. In parallel solvent effects on 4NBN absorption molar extinction coefficient also shows a maximum at this composition region. From the spectroscopic study of reactant and product and the known H-bond capacity of the mixture a rationalization that involves specific solvent H-donor interaction with the nitro group is proposed to explain the kinetic data. Present findings also show a convenient methodology to obtain strongly fluorescent imides, valuable for peptide and analogs labeling as well as for thio-naphthalimide derivatives preparations. Copyright (C) 2008 John Wiley & Sons, Ltd.

Coherence dynamics of two-mode condensates in asymmetric potentials

Detection of weak forces with an accuracy beyond the standard quantum limit holds promise both for fundamental research and for technological applications. Schemes involving ultracold atoms for such measurements are now considered to be prime candidates for increased sensitivity. In this paper we use a combination of analytical and numerical techniques to investigate the possible subshot-noise estimation of applied force fields through detection of coherence dynamics of Bose-condensed atoms in asymmetric double-well traps. Following a semiclassical description of the system dynamics and fringe visibility, we present numerical simulations of the full quantum dynamics that demonstrate the dynamical production of phase squeezing beyond the standard quantum limit. Nonlinear interactions are found to limit the achievable amount to a finite value determined by the external weak force.

The asymmetric behavior of the U.S public debt

Our main goal in this paper was to measure how e¢ cient is risk sharing between countries. In order to do so, we have used a international risk sharIn this paper we re-analyze the question of the U.S. public debt sustainability by using a quantile autoregression model. This modeling allows for testing whether the behavior of U.S. public debt is asymmetric or not. Our results provide evidence of a band of sustainability. Outside this band, the U.S. public debt is unsustainable. We also nd scal policy to be adequate in the sense that occasional episodes in which the public debt moves out of the band do not pose a threat to long run sustainability.

Central limit theorem for asymmetric kernel functionals

Asymmetric kernels are quite useful for the estimation of density functions with bounded support. Gamma kernels are designed to handle density functions whose supports are bounded from one end only, whereas beta kernels are particularly convenient for the estimation of density functions with compact support. These asymmetric kernels are nonnegative and free of boundary bias. Moreover, their shape varies according to the location of the data point, thus also changing the amount of smoothing. This paper applies the central limit theorem for degenerate U-statistics to compute the limiting distribution of a class of asymmetric kernel functionals.

The asymmetric behavior of the U.S. public debt

In this paper we re-analyze the question of the U.S. public debt sustainability by using a quantile autoregression model. This modeling allows for testing whether the behavior of U.S. public debt is asymmetric or not. Our results provide evidence of a band of sustainability. Outside this band, the U.S. public debt is unsustainable. We also find fiscal policy to be adequate in the sense that occasional episodes in which the public debt moves out of the band do not pose a threat to long run sustainability.

Equilibrium theory with asymmetric information and infinitely many states

Radner (1968) proved the existence of a competitive equilibrium for differential information economies with finitely many states. We extend this result to economies with infinitely many states of nature.

Essays on asymmetric information problems without the single-crossing property: applications to corporate finance

The objective of this dissertation is to re-examine classical issues in corporate finance, applying a new analytical tool. The single-crossing property, also called Spence-irrlees condition, is not required in the models developed here. This property has been a standard assumption in adverse selection and signaling models developed so far. The classical papers by Guesnerie and Laffont (1984) and Riley (1979) assume it. In the simplest case, for a consumer with a privately known taste, the single-crossing property states that the marginal utility of a good is monotone with respect to the taste. This assumption has an important consequence to the result of the model: the relationship between the private parameter and the quantity of the good assigned to the agent is monotone. While single crossing is a reasonable property for the utility of an ordinary consumer, this property is frequently absent in the objective function of the agents for more elaborate models. The lack of a characterization for the non-single crossing context has hindered the exploration of models that generate objective functions without this property. The first work that characterizes the optimal contract without the single-crossing property is Araújo and Moreira (2001a) and, for the competitive case, Araújo and Moreira (2001b). The main implication is that a partial separation of types may be observed. Two sets of disconnected types of agents may choose the same contract, in adverse selection problems, or signal with the same levei of signal, in signaling models.

Optimal regulation of oil fields under asymmetric information

Neste trabalho é analisada a relação entre um regulador e uma empresa petrolífera. Há várias incertezas inerentes à essa relação e o trabalho se concentra nos efeitos da assimetria de informação. Fazemos a caracterização da regulação ótima sob informação assimétrica, quando o regulador deve desenhar um mecanismo que induz a firma a revelar corretamente sua informação privada. No caso em que a rma não pode se comprometer a não romper o acordo, mostramos que o regulador pode não implementar o resultado ótimo que é obtido sob informação completa. Nesse caso, o regulador não consegue compartilhar os riscos com a firma de forma ótima. Por fim, é apresentado um exemplo, em que mostramos que a condição de Spence-Mirrlees (SMC) pode não valer. Esse resultado aparece de forma natural no modelo.

Construction of facilities under asymmetric information: do constitutional constraints matter?

This paper studies construction of facilities in a federal state under asymmetric information. A country consists of two regions, each ruled by a local authority. The federal government plans to construct a facility in one of the regions. The facility generates a local value in the host region and has spillover effects in the other region. The federal government does not observe the local value because it is the local authority's private information. 80 the federal governrnent designs an incentive-compatible mechanism, specifying if the facility should be constructed and a balanced scheme of interregional transfers to finance its cost. The federal governrnent is constitutionally constrained to respect a given leveI of each region's welfare. We show that depending upon the facility's local value and the spillover effect, the governrnent faces different incentive problems. Moreover, their existence depends crucially on how stringent constitutional constraints are. Therefore, the optimal mechanism will also depend upon these three features of the model.