Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Optimality and duality in multiobjective fractional programming involving ρ-semilocally type I-preinvex and related functions

Optimality conditions are obtained for a nonlinear fractional multiobjective programming problem involving η-semidifferentiable functions. Also, a general dual is formulated and a duality result is proved using concepts of generalized ρ-semilocally type I-preinvex functions.     

Limonene concentration in lemon (Citrus volkameriana) peel oil as a function of ripeness

The dependence of the limonene content of lemon (Citrus volkameriana) peel oil on the degree of ripeness of the fruit has been studied by using steam distillation and cold pressing to extract the oils from lemon fruit peel at different stages of maturation (green, greenish-yellow, and yellow-orange peel coloration). Samples of essential oils were analyzed by high resolution GC and GC-MS, using tetradecane as internal standard for quantitation. Forty components were detected; thirty eight were positively identified by comparison of their mass spectra (El, 70 eV) and Kováts retention indexes (determined using a non-logarithmic scale on capillary columns coated with both polar (DB-Wax) and non-polar (DB-1) stationary phases) with those of standards and with data reported in the literature. The limonene concentration reached a maximum level of 79.4% when the fruit was in the intermediate maturation stage characterized by greenish-yellow coloration.     

RECURSIVE BAIRE CLASSIFICATION AND SPEEDABLE FUNCTIONS

Using recursive variants of Baire notions of nowhere dense and meagre sets we study the topological size of speedable and infinitely often speedable functions in a machine-independent framework. We show that the set of speedable functions is not “small” whereas the set of infinitely often speedable functions is “large”. In this way we offer partial answers to a question in [4].     

Bounds for non‐periodic mixtures of infinitely many materials

We prove bounds on the homogenized coefficients for general non‐periodic mixtures of an arbitrary number of isotropic materials, in the heat conduction framework. The component materials and their proportions are given through the Young measure associated to the sequence of coefficient functions. Upper and lower bounds inequalities are deduced in terms of algebraic relations between this Young measure and the eigenvalues of the H‐limit matrix. The proofs employ arguments of compensated compactness and fine properties of Young measures. When restricted to the periodic case, we recover known bounds. Copyright © 2005 John Wiley & Sons, Ltd.     

Studies on quinones. XIV1. Oxidative demethylation of hydroquinones dimethylethers with nitric acid- impregnated manganese dioxide

The oxidative cleavage of several hydroquinones dimethylethers with nitric acid- impregnated manganese dioxide, in methylene chloride solution at room temperature, gave the corresponding quinones in 76–95% yield.     

Accurate intermolecular ground state potential of the Ar-N2 van der Waals complex

After carrying out a systematic basis set convergence study, we evaluate several ground state potential energy surfaces of the Ar-N(2) van der Waals complex at the coupled cluster singles and doubles model including connected triples corrections. We use the aug-cc-pVXZ (X=5,Q,D) and the daug-cc-pVQZ basis sets augmented with a set of 3s3p2d1f1g (denoted 33211) and 3s3p2d2f1g (denoted 33221) midbond functions, respectively. aug-cc-pVTZ-33211 results were available in the literature. The aug-cc-pV5Z-33211 (daug-cc-pVQZ-33221) surface is characterized by a T-shaped minimum at R(e)=3.709 (3.701) A and of 99.01 (102.50) cm(-1), and a linear saddle point at 4.260 (4.257) A and D(e)=75.28 (79.73) cm(-1). These results are compared with the values provided by the semiempirical potentials available, and those of previous theoretical studies. The basis set convergence of the intermolecular potentials is also analyzed. From the potentials the rovibronic spectroscopic properties are determined. We study the basis set convergence of the rotational frequencies. The binding parameters that characterized the aug-cc-pVTZ-33211 surface are reasonable, but the surface is not good enough to evaluate the microwave spectra. The aug-cc-pVQZ-33211 basis set results considerably improve the triple zeta and are close to the aug-cc-pV5Z-33211. Considering the small differences between the quadruple and the quintuple zeta surfaces, the latter results can be expected to be close to convergence. At this level the differences with respect to the accurate experimental frequencies are in the order of 0.7%. In the case of the daug-cc-pVXZ-33211,33221 (X=5,Q,T,D) series, the convergence of the interaction energies with respect to basis set improvement is not so smooth. The errors in the frequencies obtained with the daug-cc-pVQZ-33221 basis set with respect to experiment are in the order of 0.4%.     

On the theory of solvent effects

A simple electrostatic analysis is given of the virtual charge (solvaton) model to represent the environment effect on the electronic wave function of a solute immersed in a polarizable surrounding. New features of this model are found. The classical aspects are discussed and secondly the quantal implications are considered. A correct Hartree-Fock-like operator is derived which represents an electron in a molecular orbital subjected to the average effect of the other electrons and to the reaction field produced by the virtual charges on the atomic centers.A general formalism based on the preceding model is presented in appendix. The final equations have a form similar to Newton's equation to represent a solvated electron. Unlike some other theories in this field, there is no cut-off involved in the evaluation of the molecular integrals.     

Polymer-Titanium hybrids obtained by radical polymerization and Sol-Gel process

The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl acrylate) (PEtA) with TiO₂ was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl acetate (VAc). The PVAc-TiO₂ hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly affected by TiO₂ presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of TiO₂ inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network.     

Mimicking photosynthesis in a computationally designed synthetic metalloprotein

While advances in protein design have made possible the construction of protein architectures with nativelike properties and predictable structures and function, there are as of yet no examples of functional, protein-based, solar energy conversion systems. This communication describes the design and characterization of an artificial reaction center (RC) protein that closely resembles the function of the natural photosynthetic RC. The synthetic protein, designed by the protein design program CORE, participates in multiple reduction/oxidation cycles with exogenous acceptors/donors following photoexcitation. The designed metalloprotein, aRC, consists of a tetrahelical bundle functionalized with two bis-histidine bound metal cofactors: a Ru(bpy)2 moiety and a heme group. Two distinct bis-histidine binding sites were engineered for each of these metal centers. Photoexcitation of aRC results in rapid ET from the RuII complex to the heme group (kET >/= 5 x 1010 s-1) yielding a long-lived (70 ns) charge-separated state (CSS), RuIII/FeII. This long-lived CSS participates in subsequent ET reactions with exogenous donors and acceptors in multiple photocycles, thus mimicking the basic function of native photosynthetic RCs. This study illustrates the successful design and construction of a protein-based functional charge separation device using a combination of automated computational protein design and knowledge of the engineering principles of biological electron tunneling extracted from natural electron-transfer systems. To our knowledge, this represents the first example of a functional protein-based artificial reaction center.