Parameters affecting sulfonamide photo-Fenton degradation - Iron complexation and substituent group

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photo-Fenton degradation of the herbicide tebuthiuron under solar irradiation: Iron complexation and initial intermediates

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

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.

Host-guest complexation of a nitroheterocyclic compound with cyclodextrins: a spectrofluorimetric and molecular modeling study

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

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

First-order-like transition in salt-induced macroion-polyelectrolyte desorption

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates in aqueous solution

The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25°C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pKa of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO- moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions.

4-Dimethylaminocinnamylidenepyruvic acid: Synthesis, characterization and complexation with trivalent lanthanides, yttrium(III), scandium(III), thorium(IV) and uranium(VI) in aqueous solution

4-Dimethylaminocinnamylidenepyruvic acid (H-DMCP)and its sodium salt (Na-DMCP) have been synthesized and characterized. The protonation constant of DMCP as well as the stability constants of its binary 1:1 complexes with trivalent lanthanides (except Pm), Yttrium(III), Scandium(III), Thorium(IV) and Uranium(VI) were determined in an aqueous medium at 25°C and ionic strength 0.500 M. The mode of coordination of this ligand is discussed.

Copper complexation by Cyanophyta and Chlorophyta exudates

Several freshwater phytoplanktonic species (eukaryotic and prokaryotic) were grown in batch cultures up to stationary phase and quantified by chlorophyll a analysis. The complexation properties (conditional stability constant and total ligand concentration) of their exudates were investigated by complexometric titrations of the culture media using either copper or lead ion-selective electrodes. For most algae, Scatchard plot analysis of the titration data revealed two classes of copper-complexing ligands, one weaker and the other stronger. Strong copper-complexing agents were produced by Cyanophyta mainly in stationary growth phase. During exponential phase, ligand concentrations and the affinity for copper were similar for both Chlorophyta and Cyanophyta. Complexation parameters for Chlorophyta exudates were similar for both growth phases: exponential and stationary. In contrast, ligand concentrations were similar for Cyanophyta, but the conditional stability constants (the strength of association between ligand and metal) were different. Weak lead-complexing ligands were produced exclusively by two Chlorophyta.

Copper(II) and Nickel (II) Complexation Capacity of Dissolved Organic Matter from Rivers of Agricultural and Urban Areas in the State of Sao Paulo

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

Adsorption of pH-responsive polyelectrolyte chains onto spherical macroions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)