Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Mixed-Ligand Complexes of Technetium and Rhenium with Tridentate Benzamidines and Bidentate Benzoylthioureas

Mixed-ligand complexes of technetium(V) or rhenium(V) containing tridentate N-[(dialkylamino)(thiocarbonyl)]benzamidine (H(2)L(1)) and bidentate N,N-dialkyl-N`-benzoylthiourea (HL(2)) ligands were formed in high yields when (NBu(4))[MOCl(4)] (M = Tc or Re) or [ReOCl(3)(PPh(3))(2)] was treated with mixtures of the proligands. Other approaches for the synthesis of the products are reactions of [MOCl(L(1))] complexes with HL(2) or compounds of the-composition [ReOCl(2)(PPh(3))(L(2))] with H(2)L(1). The resulting air-stable [MO(L(1))(L(2))] complexes possess potential for the development of metal-based radiopharmaceuticals. [TcO(L(1))(L(2))] complexes are readily reduced by PPh3 with formation of [Tc(L(1))(L(2))(PPh(3))]. The resulting Tc(III) complexes undergo two almost-reversible oxidation steps corresponding to one-electron transfer processes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Evidence for Reductive Genome Evolution and Lateral Acquisition of Virulence Functions in Two Corynebacterium pseudotuberculosis Strains

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Generalized linear mixed models for the genetic evaluation of binary reproductive traits: a simulation study

The objective of this study was to evaluate the use of probit and logit link functions for the genetic evaluation of early pregnancy using simulated data. The following simulation/analysis structures were constructed: logit/logit, logit/probit, probit/logit, and probit/probit. The percentages of precocious females were 5, 10, 15, 20, 25 and 30% and were adjusted based on a change in the mean of the latent variable. The parametric heritability (h²) was 0.40. Simulation and genetic evaluation were implemented in the R software. Heritability estimates (ĥ²) were compared with h² using the mean squared error. Pearson correlations between predicted and true breeding values and the percentage of coincidence between true and predicted ranking, considering the 10% of bulls with the highest breeding values (TOP10) were calculated. The mean ĥ² values were under- and overestimated for all percentages of precocious females when logit/probit and probit/logit models used. In addition, the mean squared errors of these models were high when compared with those obtained with the probit/probit and logit/logit models. Considering ĥ², probit/probit and logit/logit were also superior to logit/probit and probit/logit, providing values close to the parametric heritability. Logit/probit and probit/logit presented low Pearson correlations, whereas the correlations obtained with probit/probit and logit/logit ranged from moderate to high. With respect to the TOP10 bulls, logit/probit and probit/logit presented much lower percentages than probit/probit and logit/logit. The genetic parameter estimates and predictions of breeding values of the animals obtained with the logit/logit and probit/probit models were similar. In contrast, the results obtained with probit/logit and logit/probit were not satisfactory. There is need to compare the estimation and prediction ability of logit and probit link functions.

Wannier functions of isolated bands in one-dimensional crystals

We present a simple procedure to obtain the maximally localized Wannier function of isolated bands in one-dimensional crystals with or without inversion symmetry. First, we discuss the generality of dealing with real Wannier functions. Next, we use a transfer-matrix technique to obtain nonoptimal Bloch functions which are analytic in the wave number. This produces two classes of real Wannier functions. Then, the minimization of the variance of the Wannier functions is performed, by using the antiderivative of the Berry connection. In the case of centrosymmetric crystals, this procedure leads to the Wannier-Kohn functions. The asymptotic behavior of the Wannier functions is also analyzed. The maximally localized Wannier functions show the expected exponential and power-law decays. Instead, nonoptimal Wannier functions may show reduced exponential and anisotropic power-law decays. The theory is illustrated with numerical calculations of Wannier functions for conduction electrons in semiconductor superlattices.

Confinement of spin-0 and spin-1/2 particles in a mixed vector-scalar coupling with unequal shapes for the potentials

The Klein - Gordon and the Dirac equations with vector and scalar potentials are investigated under a more general condition, V-v = V-s + constant. These isospectral problems are solved in the case of squared trigonometric potential functions and bound states for either particles or antiparticles are found. The eigenvalues and eigenfunctions are discussed in some detail. It is revealed that a spin-0 particle is better localized than a spin-1/2 particle when they have the same mass and are subjected to the same potentials.

Bound states of bosons and fermions in a mixed vector-scalar coupling with unequal shapes for the potentials

The Klein - Gordon and the Dirac equations with vector and scalar potentials are investigated under a more general condition, V(v) + V(s) = constant. These intrinsically relativistic and isospectral problems are solved in the case of squared hyperbolic potential functions and bound states for either particles or antiparticles are found. The eigenvalues and eigenfuntions are discussed in some detail and the effective Compton wavelength is revealed to be an important physical quantity. It is revealed that a boson is better localized than a fermion when they have the same mass and are subjected to the same potentials.

Heat transfer in laminar flow of non-Newtonian fluids in ducts of elliptical section

Laminar forced convection inside tubes of various cross-section shapes is of interest in the design of a low Reynolds number heat exchanger apparatus. Heat transfer to thermally developing, hydrodynamically developed forced convection inside tubes of simple geometries such as a circular tube, parallel plate, or annular duct has been well studied in the literature and documented in various books, but for elliptical duct there are not much work done. The main assumption used in this work is a laminar flow of a power flow inside elliptical tube, under a boundary condition of first kind with constant physical properties and negligible axial heat diffusion (high Peclet number). To solve the thermally developing problem, we use the generalized integral transform technique (GITT), also known as Sturm-Liouville transform. Actually, such an integral transform is a generalization of the finite Fourier transform where the sine and cosine functions are replaced by more general sets of orthogonal functions. The axes are algebraically transformed from the Cartesian coordinate system to the elliptical coordinate system in order to avoid the irregular shape of the elliptical duct wall. The GITT is then applied to transform and solve the problem and to obtain the once unknown temperature field. Afterward, it is possible to compute and present the quantities of practical interest, such as the bulk fluid temperature, the local Nusselt number and the average Nusselt number for various cross-section aspect ratios. (C) 2006 Elsevier. SAS. All rights reserved.

Friction factors, convective heat transfer coefficients and the Colburn analogy for industrial sugarcane juices

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nonautonomous mixed mKdV-sinh-Gordon hierarchy

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

Temperature dependence of photoinduced birefringence in mixed Langmuir-Blodgett (LB) films of azobenzene-containing polymers

The temperature dependence of photoinduced birefringence was investigated for mixed Langmuir-Blodgett (LB) films from the homopolymer poly[4'-[[2-(methacryloyloxy)ethyl]ethyl-amino]-2-chloro-4-nitroazobenzene] (HPDR13) and cadmium stearate (Cdst) and from the copolymer 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) and CdSt. Birefringence was achieved by impinging a linearly polarized light on the LB films. The maximum birefringence achieved decreased with temperature as thermal relaxation of the chromophores was facilitated. The buildup curves for birefringence were fitted with biexponential functions representing distinctly different mechanisms with time constants. The first, fast process is thermally activated and may be represented by an Arrhenius process. The decay of birefringence after switching off the laser source was described by a Kohlraush-Williams-Watts (KWW) function, consistent with a distribution of relaxation times for the polymer system. Activation energies were obtained from Arrhenius plots of the rate constant of the exponential functions and KWW function, which showed that the buildup of birefringence was very similar for the two polymer systems. The decay, however, was slower for the LB film from MMA-DR13/CdSt. (C) 2002 Published by Elsevier B.V. Ltd.

Optimal switch allocation for automatic load transfer in distribution substations

This work proposes a methodology for optimized allocation of switches for automatic load transfer in distribution systems in order to improve the reliability indexes by restoring such systems which present voltage classes of 23 to 35 kV and radial topology. The automatic switches must be allocated on the system in order to transfer load remotely among the sources at the substations. The problem of switch allocation is formulated as nonlinear constrained mixed integer programming model subject to a set of economical and physical constraints. A dedicated Tabu Search (TS) algorithm is proposed to solve this model. The proposed methodology is tested for a large real-life distribution system. © 2011 IEEE.

Optimal conductor size selection and reconductoring in radial distribution systems using a mixed-integer LP approach

This paper presents a mixed-integer linear programming model to solve the conductor size selection and reconductoring problem in radial distribution systems. In the proposed model, the steady-state operation of the radial distribution system is modeled through linear expressions. The use of a mixed-integer linear model guarantees convergence to optimality using existing optimization software. The proposed model and a heuristic are used to obtain the Pareto front of the conductor size selection and reconductoring problem considering two different objective functions. The results of one test system and two real distribution systems are presented in order to show the accuracy as well as the efficiency of the proposed solution technique. © 1969-2012 IEEE.

A mixed-integer linear programming approach for optimal type, size and allocation of distributed generation in radial distribution systems

This paper presents a mixed-integer linear programming approach to solving the problem of optimal type, size and allocation of distributed generators (DGs) in radial distribution systems. In the proposed formulation, (a) the steady-state operation of the radial distribution system, considering different load levels, is modeled through linear expressions; (b) different types of DGs are represented by their capability curves; (c) the short-circuit current capacity of the circuits is modeled through linear expressions; and (d) different topologies of the radial distribution system are considered. The objective function minimizes the annualized investment and operation costs. The use of a mixed-integer linear formulation guarantees convergence to optimality using existing optimization software. The results of one test system are presented in order to show the accuracy as well as the efficiency of the proposed solution technique.© 2012 Elsevier B.V. All rights reserved.