Motional heterogeneities in siloxane/poly(ethylene glycol) ormolyte nanocomposites studied by C-13 solid-state exchange NMR

C-13 exchange solid-state NMR methods were used to study two families of siloxane/poly-(ethylene glycol) hybrid materials: Types I and II, where the polymer chains interact with the inorganic phase through physical (hydrogen bonds or van der Waals forces) or chemical (covalent bonds) interactions, respectively. These methods were employed to analyze the effects of the interactions between the organic and inorganic phases on the polymer dynamics in the milliseconds to seconds time scale, which occurs at temperatures below the motional narrowing of the NMR line width and around the polymer glass transition. Motional heterogeneities associated with these interactions and evidence of both small and large amplitude motions were directly observed for both types of hybrids. The results revealed that the hindrance to the slow molecular motions of the polymer chains due to the siloxane structures depends on the chain length and the nature of the interaction between the organic and inorganic phases.

Environmental coordination chemistry: Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution. Ionic medium effects on equilibrium constants

The molar single activity coefficients associated with propionate ion (Pr) have been determined at 25 degrees C and ionic strengths comprised between 0.300 and 3.00 M, adjusted with NaClO4, as background electrolyte. The investigation was carried out potentiometrically by using a second class Hg/Hg2Pr2 electrode. It was found that the dependence of propionate activity coefficients as a function of ionic strength (I) can be assessed through the following empirical equation: log y(Pr) = -0.185 I-3/2 + 0.104 I-2. Next, simple equations relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous solution, at 25 degrees C, as a function of ionic strength were derived, allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as parameters associated with activity coefficients of the complex species in the equilibria are estimated. The body of results shows that the proposed calculation procedure is very consistent with critically selected experimental data.

Exchange interaction effects in the ESR spectra of Eu2+ in LaB6

The electron spin resonance (ESR) spectra of Eu2+ (4f(7), S = 7/2) in LaB6 single crystal show a single Dysonian resonance for the localized Eu2+ magnetic moments. It is shown that the Eu2+ ions are covalent exchange coupled to the (B) 2p-like host conduction electrons. (c) 2007 Elsevier B.V. All rights reserved.

Ionic medium effects on equilibrium constants .2. Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution

Simple equations were derived relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous sodium perchlorate media, at 25 degrees C, as a function of ionic strength (I), allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as activity coefficients of the species involved in the equilibria were estimated. The results show that the proposed calculation procedure is very consistent with critically selected experimental data.

Lability of heavy metal species in aquatic humic substances characterized by ion exchange with cellulose phosphate

Labile metal species in aquatic humic substances (HSs) were characterized by ion exchange on cellulose phosphate (CellPhos) by applying an optimized batch procedure. The HSs investigated were pre-extracted from humic-rich waters by ultrafiltration and a resin XAD 8 procedure. The HS-metal species studied were formed by complexation with Cd(II), Ni(II), Cu(II), Mn(II) and Pb(II) as a function of time and the ratio ions to HSs. The kinetics and reaction order of this exchange process were studied. At the beginning (<3 min), the labile metal fractions are separated relatively quickly. After 3 min, the separation of the metal ions proceeds with uniform half-lives of about 12-14 min, revealing rather slow first-order kinetics. The metal exchange between HSs and CellPhos exhibited the following order of metal lability with the studied HSs: Cu > Pb > Mn > Ni > Cd. The required metal determinations were carried out by atomic absorption spectrometry.

Gas exchange in lisianthus plants (Eustoma grandiflorum) submitted to different doses of nitrogen

The effect of different doses of nitrogen (N) on gas exchange, relative chlorophyll (Chl) amount, and the content of N in the aerial biomass of lisianthus was evaluated. The treatments consisted of six different concentrations of N (50, 100, 150, 200, 250, and 300 g m(-3) noted as N-50, N-100, N-150, N-200, N-250, and N-300, respectively), applied through the fertirrigation technique. N-250 and N-300 induced increase in the contents of foliar Chl and N in the aerial biomass, that in turn contributed to an increase of photosynthetic activity in lisianthus.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Exchange narrowing effects in the EPR linewidth of Gd diluted in Ce compounds

Anomalous thermal behavior on the EPR linewidths of Gd impurities diluted in Cc compounds has been observed. In metals, the local magnetic moment EPR linewidth, Delta H, is expected to increase linearly with the temperature. In contrast, in CexLa1-xOs2 the Gd EPR spectra show a nonlinear increase. In this work, the mechanisms that are responsible for the thermal behavior of the EPR lines in CexLa1-xOs2 are examined. We show that the exchange interaction between the local magnetic moments and the conduction electrons are responsible for the narrowing of the spectra at low temperatures. At high temperatures, the contribution to the linewidth of the exchange interaction between the local magnetic moments and the Ce ions has an exponential dependence on the excitation energy of the intermediate valent ions. A complete fitting of the EPR spectra for powdered samples is obtained, (C) 1998 American Institute of Physics. [S0021-8979(98)39911-9].

CHIRAL BACKGROUND FOR THE 2-PION EXCHANGE NUCLEAR-POTENTIAL - A PARAMETRIZED VERSION

We argue that the minimal chiral background for the two-pion exchange nucleon-nucleon (NN) interaction has nowadays a rather firm conceptual basis, which entitles it to become a standard ingredient of any modern potential. In order to facilitate applications, we present a parametrized version of a configuration space potential derived previously. We than use it to assess the phenomenological contents of some existing NN potentials.

INFLUENCE OF HIGH MICROWAVE DIELECTRIC-CONSTANTS ON THE LINESHAPE OF CONDUCTION-ELECTRON SPIN-RESONANCE

Some synthetic metals show in addition to good conductivity, high microwave dielectric constants. In this work, it is shown how conduction-electron spin resonance(CESR) lineshape can be affected by these high constants. The conditions for avoiding these effects in the CESR measurements are discussed as well as a method for extracting microwave dielectric constants from CESR lines. (C) 1995 Academic Press, Inc.

Ionic medium effects on equilibrium constants .1. Proton, copper(II), cadmium(II), lead(II) and acetate activity coefficients in aqueous solution

The molar single ion activity coefficients associated with hydrogen, copper(II), cadmium(II) and lead(II) ions were determined at 25 degrees C and ionic strengths between 0.100 and 3.00 M (NaClO4), whereas for acetate the ionic strengths were fixed between 0.300 and 2.00 M, held with the same inert electrolyte. The investigation was carried out potentiometrically by using proton-sensitive glass, copper, cadmium and lead ion-selective electrodes and a second-class Hg\Hg-2(CH3COO)(2) electrode. It was found that the activity coefficients of these ions (y(i)) can be assessed through the following empirical equations:log y(H) = -0.542I(0.5) + 0.451I; log y(Cu) = -1.249I(0.5) + 0.912I; log y(Cd) = -0.829I(0.5) + 0.448I(1.5);log y(Pb) = -0.404I(0.5) + 0.117I(2); and log y(Ac) = 0.0370I .

Effect of spin-polarized subbands in the inhomogeneous hole gas providing the indirect exchange in GaMnAs bilayers

The magnetic order resulting from the indirect exchange in the metallic phase of a (Ga,Mn)As/GaAs double layer structure is studied via Monte Carlo simulation. The polarization of the hole gas is taken into account, establishing a self-consistency between the magnetic order and the electronic structure. The Curie-Weiss temperatures calculated for these low-dimensional systems are in the range of 50-80 K, and the dependence of the transition temperature with the GaAs separation layer is established. (C) 2003 Published by Elsevier B.V.

Er3+-doped germanate glasses for active waveguides prepared by Ag+/K+ <-> Na+ ion-exchange

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Irradiance stress responses of gas exchange and antioxidant enzyme contents in pariparoba [Pothomorphe umbellata (L.) Miq.] plants

We evaluated the growth and development of the medicinal species Pothomorphe umbellata ( L.) Miq. under different shade levels ( full sun and 30, 50, and 70 % shade, marked as I(100), I(70), I(50), and I(30), respectively) and their effects on gas exchange and activities of antioxidant enzymes. Photosynthetically active radiation varied from 1 254 mu mol m(-2) s(-1) at I(100) to 285 mu mol m(-2) s(-1) at I(30). Stomatal conductance, net photosynthetic rate, and relative chlorophyll (Chl) content were maximal in I(70) plants. Plants grown under I(100) produced leaves with lower Chl content and signs of chlorosis and necrosis. These symptoms indicated Chl degradation induced by the generation of reactive oxygen species. Stress related antioxidant enzyme activities ( Mn-SOD, Fe-SOD, and Cu/Zn-SOD) were highest in I(100) plants, whereas catalase activity was the lowest. Hence P. umbellata is a shade species ( sciophyte), a feature that should be considered in reforestation programs or in field plantings for production of medicinal constituents.