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Photophysical and Complexation Studies of Chloro-Aluminum Phthalocyanine with Beta-Cyclodextrin and Hydroxypropyl-Beta-Cyclodextrin

SILVA, Angelo Roncalli A.; SIMIONI, Andreza R.; TEDESCO, Antonio C.
Fonte: AMER SCIENTIFIC PUBLISHERS Publicador: AMER SCIENTIFIC PUBLISHERS
Tipo: Artigo de Revista Científica
ENG
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A variety of nanostructures are being investigated as functional drug carriers for treatment of a wide range of diseases, most notably cardiovascular defects, autoimmune diseases, and cancer. The aim of this present contribution is to evaluate potentially applicable nanomaterials in the diagnosis and treatment of cancer due to their photophysical and photobiological properties and complexation behavior. The delivery systems consisted of chloro-aluminum phthalocyanine associated with beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin. The preparation of the complex and its stoichiometry in an ethanol/buffer (3:1) solution were studied by spectroscopic techniques, which were defined as 1:2. The inclusion complex in the nanometer scale was observed on the basis of changes to the spectroscopic properties. The singlet oxygen production and complex photophysical parameters were determined by measuring luminescence at 1270 nm and by steady state and time resolved spectroscopic, respectively. The preparation of the complex was tested and analyzed with regard to cellular damage by visible light activation. The inclusion complex showed a higher singlet oxygen quantum yield compared with other systems and other photoactive dyes. There was also a reduction in the fluorescence quantum yield compared with the results obtained for zinc phthalocyanine in organic medium. The results reported clearly that the inclusion complex chloro-aluminum phthalocyanine/cyclodextrin showed some changes in its spectroscopy properties leading to better biodistribution and biocompatibility with a potential application in photodynamic therapy...

Ionic Recognition by 7-Nitro-1,3,5-triaza Adamantane: First Thermodynamic Study

NAMOR, Angela F. Danil de; NWOGU, Nwanyinnaya A.; ZVIETCOVICH-GUERRA, Jorge A.; PIRO, Oscar E.; CASTELLANO, Eduardo Ernesto
Fonte: AMER CHEMICAL SOC Publicador: AMER CHEMICAL SOC
Tipo: Artigo de Revista Científica
ENG
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A thermodynamic study involving 7-nitro-1,3,5-triaza adamantane, 1, and its interaction with metal cations in nonaqueous media is first reported. Solubility data of 1 in various solvents were used to derive the standard Gibbs energies of solution, Delta G(s)degrees in these solvents. The effect of solvation in the different media was assessed from the Gibbs energy of transfer taking acetonitrile as a reference solvent. (1)H NMR studies of the interaction of 1 and metal cations were carried out in CD(3)CN and CD(3)OD and the data are reported. Conductance measurements revealed that this ligand forms lead(II) or zinc complexes of 1: 1 stoichiometry in acetonitrile. It also revealed a stoichiometry of two molecules of 1 per mercury(II) and two cadmiu (II) ions per molecule of 1. The addition of silver salt to 1 led to the precipitation of the silver-1 complex which was isolated and characterized by X-ray crystallography. At variance with conductance measurements in solution, in the solid state the X-ray structure show`s a 1:1 stoichiometry in the Hg(II) complex. The themiodynamics of complexation of 1 and these cations provide a quantitative assessment of the selective behavior of this ligand for ions of environmental relevance.

"Estudo do processo de complexação de calixarenos com íons metálicos e espécies neutras por simulações de dinâmica molecular" ; A study of the complexation process of calixarenes with metallic ions and neutral species from molecular dynamic simulations

Araujo, Alexandre Suman de
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 20/09/2006 PT
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Apresentamos uma série de estudos, baseados em simulações de Dinâmica Molecular no vácuo e em solução, sobre o processo de complexação das supramoléculas tetraethylester p-tert-butyl calix[4]arene (CLE) e tetramethylketone p-tert-butyl calix[4]arene (CLC) com os íons Pb2+ e Cd2+ e espécies neutras. Os modelos para as moléculas de calixareno e do solvente foram baseados no campo de forças OPLS-AA. Os parâmetros para os íons foram desenvolvidos a partir de uma metodologia de ajuste de valores de modo a reproduzirem simultaneamente propriedades termodinâmicas e estruturais obtidas experimentalmente ou por cálculos de QM/MM. As simulações no estado líquido nos mostraram que o CLE aprisiona os íons de maneira mais eficiente que o CLC, formando complexos mais estáveis. A complexação do íon desencadeia um efeito alostérico em ambos os calixarenos estudados, permitindo a complexação de uma molécula de acetonitrila na cavidade hidrofóbica estabilizando o complexo. Nas simulações com o CLC observamos que a complexação da acetonitrila é necessária para manter o íon ligado à cavidade hidrofílica, evidenciando a dependência desses complexos com esse solvente em específico. Apesar de observarmos que o CLE apresenta maior afinidade com os íons Pb2+ e Cd2+ que o CLC...

Atividade antioxidante da vanilina e do ácido vanílico e o efeito da complexação por proteínas do soro do leite na desativação de radicais e ferrilmioglobina em condições simulando o trato gastrointestinal; Antioxidant activity of vanillin and vanillic acid and the effect of complexation by milk whey proteins in the deactivation of radicals and ferrylmyoglobin under conditions simulating the gastrointestinal tract

Libardi, Silvia Helena
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 23/07/2010 PT
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O presente trabalho procurou investigar influência da presença de proteínas do soro do leite na atividade antioxidante da vanilina e ácido vanílico frente ao radical DPPH• e a espécie de ferro hipervalente ferrilmioglobina MbFe(IV)=O em meio simulando o trato gastrointestinal. A constante de associação (KA) entre a vanilina e a β-lactoglobulina (BLG) foi determinada utilizando-se as técnicas de espectroscopia de emissão molecular (KA = 400 ± 12·102 L·mol-1) e microcalorimétria (KA = 5,6±0,3·102 L·mol-1) ambas em tampão fosfato com CH+ = 10-7,4 mol·L-1 e força iônica 0,32 (NaCl). Para a interação entre a vanilina e albumina de soro bovino (BSA) encontrou-se o valor de 340 ± 13·102 L·mol-1 em meio de tampão fosfato com CH+ = 10-6,4 mol·L-1 e força iônica 0,32 (NaCl), obtido por espectroscopia de emissão molecular. Constatou-se pela técnica de microcalorimetria que a complexação possui caráter exotérmico e as contribuições de interações hidrofóbicas para a complexação são fracas. A reatividade da vanilina e ácido vanílico com o radical DPPH• foi investigada em meio de emulsão aquosa Tween-20® com CH+ = 10-2...

Avaliação da interação entre galectina-1 e zinco e suas potenciais implicações estruturais e funcionais; Evaluation of the interaction between Galectin-1 and Zinc and their potential structural and functional implications

Silveira, Willian Abraham da
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 01/07/2011 PT
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Introdução: A Galectina-1 (Gal-1) é uma proteína multifuncional capaz de reconhecer, de modo específico, glicanas compostas por resíduos de -galactosídeos, por meio de domínios de reconhecimento de carboidrato (CRD). A Gal-1 é um homodímero de 14.900 daltons, pI = 5.6, apresenta uma topologia molecular do tipo jelly-roll composto por duas folhas- anti-paralelas. Além disso, esta proteína não apresenta peptídeo sinal e possui 6 cisteínas, 7 ácidos glutâmicos, 9 ácidos aspárticos e 4 histinas por monômero. A Gal-1 liga-se a diferentes moléculas biológicas contidas nas superfícies celulares, núcleo e componentes da matriz extracelular. O zinco é um importante metal em sistemas biológicos. Aproximadamente 10% do proteoma humano é potencialmente capaz de complexar zinco. Este íon exibe propriedades adequadas tanto para funções catalíticas, quanto estruturais em proteínas. Os sítios de ligação a zinco, nas proteínas, podem ser divididos em catalíticos, estruturais, co-catalíticos e sítios na interface protéica. Geralmente, os resíduos de cisteína, histidina, ácido glutâmico e ácido aspártico são alvos preferênciais de interação com Zn. Há na literatura dados que mostram a interação da Gal-1 humana com íons orgânicos...

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

Batista, Ana Paula S.; Pupo Nogueira, Raquel F.
Fonte: Elsevier B.V. Sa Publicador: Elsevier B.V. Sa
Tipo: Artigo de Revista Científica
ENG
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); The photo-Fenton degradation of the sulfonamide antibiotics sulfadiazine (SDZ) and sulfathiazole (STZ) mediated by Fe(III)-oxalate was studied in this work. The influence of iron complexation. H2O2 concentration and pH on the initial SDZ and STZ degradation rate was evaluated. Degradation of both antibiotics is drastically improved in the presence of Fe(III)-oxalate in comparison to free iron, achieving complete degradation after 8 min irradiation at pH 2.5 in the presence of 5 mM H2O2 (equivalent to H2O2/antibiotic = 50). It was also possible to extend pH range of the photo-Fenton reaction by the use of Fe(III)-oxalate reaching more the 70% degradation at pH 6, however without significant mineralization. Comparison of the degradation kinetics of both sulfonamides indicated higher recalcitrance of STZ due to the lower electron density of its thiazol ring in relation to pyrimidine ring in SDZ. (C) 2012 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

Romao, LPC; Castro, G. R.; Rosa, A. H.; Rocha, J. C.; Padilha, P. M.; Silva, H. C.
Fonte: Springer Publicador: Springer
Tipo: Artigo de Revista Científica Formato: 1097-1100
ENG
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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.

Copper complexation by Cyanophyta and Chlorophyta exudates

Lombardi, A. T.; Vieira, A. A. H.
Fonte: Universidade Estadual Paulista Publicador: Universidade Estadual Paulista
Tipo: Artigo de Revista Científica Formato: 118-125
ENG
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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.

X-ray fluorescence determination of adsorbed copper on activated charcoal after glycerin complexation

Bueno,Maria Izabel Maretti Silveira; Amaral,Lêda Cristina do
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/07/1998 EN
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X-This work shows an alternative method to copper determination by X-Ray Fluorescence (XRF). Since copper concentration in natural waters is not enough to reach XRF detection limit, a liquid-solid preconcentration procedure was proposed. Glycerin was used to complex the metal increasing its adsorption on activated charcoal. The solid phase was used to XRF determination. Several parameters were evaluated, such as, the complexation pH, the charcoal adsorption limit and the glycerin concentration. The interferences are lead and bismuth and the sensitivities decreased in the order Cu2+, Bi3+ and Pb2+. The advantages of the method are its simplicity, low cost and low spectral interference.

An Ab Initio MP2 Study of HCN-HX Hydrogen Bonded Complexes

Araújo,Regiane C.M.U.; Ramos,Mozart N.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/09/1998 EN
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An ab initio MP2/6-311++G** study has been performed to obtain geometries, binding energies and vibrational properties of HCN-HX H-bonded complexes with X = F, Cl, NC, CN and CCH. These MP2/6-311++G** results have revealed that: (i) the calculated H-bond lengths are in very good agreement with the experimental ones; (ii) the H-bond strength is associated with the intermolecular charge transfer and follows the order: HCN-HNC ~ HCN-HF > HCN-HCl ~ HCN-HCN > HCN-HCCH; (iii) BSSE correction introduces an average reduction of 2.4 kJ/mol on the MP2/6-311++G** binding energies, i.e. 11% of the uncorrected binding energy; (iv) the calculated zero-point energies reduce the stability of these complexes and show a good agreement with the available experimental values; (v) the H-X stretching frequency is shifted downward upon H-bond formation. This displacement is associated with the H-bond length; (vi) The more pronounced effect on the infrared intensities occurs with the H-X stretching intensity. It is much enhanced after complexation due to the charge-flux term; (vii) the calculated intermolecular stretching frequencies are in very good agreement with the experimental ones; and, finally, (viii) the results obtained for the HCN-HX complexes follow the same profile as those found for the acetylene-HX series but...

Preconcentration and Determination of Copper and Zinc in Natural Water Samples by ICP-AES After Complexation and Sorption on Amberlite XAD-2

Ferreira,Sérgio Luis Costa; Santos,Hilda Costa dos; Ferreira,Janeide Reis; Araújo,Neyla Margarida Lopo de; Costa,Antônio Celso Spinola; Jesus,Djane Santiago de
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/12/1998 EN
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The present paper describes a procedure for separation, preconcentration and sequential determination of trace amounts of copper and zinc in natural water samples, by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The proposed method is based on the complexation of copper(II) and zinc(II) ions by 1-(2-thiazolylazo)-2-naphthol (TAN) and sorption on to Amberlite XAD-2 resin. Parameters such as: TAN amount, pH effect on the complexation and sorption of TAN complexes, agitation time for complete sorption, concentration of metal ion, mass of Amberlite XAD-2, desorption of metal ions from XAD-2 resin and sample volume were studied. The results demonstrated that the copper(II) and zinc(II) ions, in the range of 0.10 to 100.00 mug, contained in a solution sample volume of 400 mL, in the pH range of 5.7 to 8.3, on the form of TAN complexes had been quantitatively retained on to XAD-2 resin. The shaking time required for sorption is 1 h using a resin mass of 1.4 g. The solution for determination of copper and zinc by ICP-AES is obtained, after desorption of the ions from the XAD-2 resin, using 5 mL of 2 mol L-1 hydrochloric acid and shaking the system for 5 min. The procedure was applied to the determination of copper and zinc in several natural water samples. The standard addition technique was applied and the obtained recoveries revealed that the proposed procedure has a good accuracy. A high enrichment factor (80) and simplicity are the main advantages in this analytical protocol.

Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal*

Song, Ming-zhi; Zhu, Lan-ying; Gao, Xi-ke; Dou, Jian-min; Sun, De-zhi
Fonte: Zhejiang University Press Publicador: Zhejiang University Press
Tipo: Artigo de Revista Científica
EN
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Thermodynamic parameters of complexation of naphto-15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.

Predicting Complexation Thermodynamic Parameters of β-Cyclodextrin with Chiral Guests by Using Swarm Intelligence and Support Vector Machines

Prakasvudhisarn, Chakguy; Wolschann, Peter; Lawtrakul, Luckhana
Fonte: Molecular Diversity Preservation International (MDPI) Publicador: Molecular Diversity Preservation International (MDPI)
Tipo: Artigo de Revista Científica
Publicado em 14/05/2009 EN
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The Particle Swarm Optimization (PSO) and Support Vector Machines (SVMs) approaches are used for predicting the thermodynamic parameters for the 1:1 inclusion complexation of chiral guests with β-cyclodextrin. A PSO is adopted for descriptor selection in the quantitative structure-property relationships (QSPR) of a dataset of 74 chiral guests due to its simplicity, speed, and consistency. The modified PSO is then combined with SVMs for its good approximating properties, to generate a QSPR model with the selected features. Linear, polynomial, and Gaussian radial basis functions are used as kernels in SVMs. All models have demonstrated an impressive performance with R2 higher than 0.8.

Complexation of Arsenite with Dissolved Organic Matter: Conditional Distribution Coefficients and Apparent Stability Constants

Liu, Guangliang; Cai, Yong
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /11/2010 EN
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The complexation of arsenic (As) with dissolved organic matter (DOM), although playing an important role in regulating As mobility and transformation, is poorly characterized, as evidenced by scarce reporting of fundamental parameters of As-DOM complexes. The complexation of arsenite (AsIII) with Aldrich humic acid (HA) at different pHs was characterized using a recently developed analytical technique to measure both free and DOM-bound As. Conditional distribution coefficient (KD), describing capacity of DOM in binding AsIII from the mass perspective, and apparent stability constant (Ks), describing stability of resulting AsIII-DOM complexes, were calculated to characterize AsIII-DOM complexation. Log KD of AsIII ranged from 3.7 to 2.2 (decreasing with increase of As/DOM ratio) at pH 5.2, from 3.6 to 2.6 at pH 7, and from 4.3 to 3.2 at pH = 9.3, respectively. Two-site ligand binding models can capture the heterogeneity of binding sites and be used to calculate Ks by classifying the binding sites into strong (S1) and weak (S2) groups. Log Ks for S1 sites are 7.0, 6.5, and 5.9 for pH 5.2, 7, and 9.3, respectively, which are approximately 1–2 orders of magnitude higher than for weak S2 sites. The results suggest that AsIII complexation with DOM increases with pH...

Interaction of artesunate with β-cyclodextrin: Characterization, thermodynamic parameters, molecular modeling, effect of PEG on complexation and antimalarial activity

Chadha, Renu; Gupta, Sushma; Shukla, Geeta; Jain, D.V.S.; Pissurlenkar, Raghuvir R.S.; Coutinho, Evans C.
Fonte: Elsevier Publicador: Elsevier
Tipo: Artigo de Revista Científica
Publicado em 04/08/2011 EN
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Inclusion of artesunate in the cavity of β-cyclodextrin (β-CD) as well as its methyl and hydroxypropyl derivatives was investigated experimentally and by molecular modeling studies. The effect of PEG on the inclusion was also studied. A 1:1 stoichiometry was indicated by phase-solubility studies both in the presence and absence of PEG and suggested by the mass spectrometry. The mode of inclusion was supported by 2D NMR and results were further verified by docking studies utilizing Fast Rigid Exhaustive Docking acronym. The thermodynamic parameters were determined for both binary and ternary systems using solution calorimetry and were found to be best for the methyl-β-cyclodextrin (Me-β-CD) system. However, the presence of PEG improves the complexation ability as evident from elevation in the numerical value of the stability constant (K). Solubility and dissolution profile of binary complex is enhanced in the presence of PEG, which is approximately at par with drug Me-β-CD complexes. In vivo studies showed 100% survivability in artesunate–Me-β-CD complexes.

Obtenção de ferrita de cobalto através de dois métodos de síntese: método de complexação combinando EDTA/Citrato e método hidrotérmico; Obtaining cobalt ferrite through two synthesis methods: Complexation Method Conbining EDTA/Citrate and Hydrothermal Method

Medeiros, Indira Aritana Fernandes de
Fonte: Universidade Federal do Rio Grande do Norte; BR; UFRN; Programa de Pós-Graduação em Engenharia Química; Pesquisa e Desenvolvimento de Tecnologias Regionais Publicador: Universidade Federal do Rio Grande do Norte; BR; UFRN; Programa de Pós-Graduação em Engenharia Química; Pesquisa e Desenvolvimento de Tecnologias Regionais
Tipo: Dissertação Formato: application/pdf
POR
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In this work it was synthesized and characterized the cobalt ferrite (CoFe2O4) by two methods: complexation combining EDTA/Citrate and hydrothermal investigating the influence of the synthesis conditions on phase formation and on the crystallite size. The powders were mainly characterized by x-ray diffraction. In specific cases, it was also used scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), x-ray fluorescence (XRF) and isotherms of adsorption and desorption of nitrogen (BET method). The study of the crystallite size was based on the interpretation of x-ray diffractograms obtained and estimated by the method of Halder-Wagner-Scherrer and Langford. An experimental design was made in order to assist in quantifying the influence of synthesis conditions on the response variables. The synthesis parameters evaluated in this study were: pH of the reaction medium (8, 9 and 10), the calcination temperature (combined complexation method EDTA/Citrate 600°C, 800°C and 1000°C), synthesis temperature (hydrothermal method 120°C, 140°C and 160°C), calcination time (combined complexation method EDTA/Citrate - 2, 4 and 6 hours) and time of synthesis (hydrothermal method 6, 15 and 24 hours). By the hydrothermal method was possible to produce mesoporous powders with high purity...

Identifying key controls on the behaviour of an acidic-U(VI) plume in the Savannah River Site using reactive transport modeling

Bea, Sergio Andrés; Wainwright, Haruko; Spycher, Nicolas; Faybishenko, Boris; Hubbard, Susan S.; Denham, Miles E.
Fonte: Elsevier Publicador: Elsevier
Tipo: info:eu-repo/semantics/article; info:ar-repo/semantics/artículo; info:eu-repo/semantics/publishedVersion Formato: application/pdf
ENG
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Acidic low-level waste radioactive waste solutions were discharged to three unlined seepage basins at the F-Area of the Department of Energy (DOE) Savannah River Site (SRS), South Carolina, USA, from 1955 through 1989. Despite of many years of active remediation, the groundwater remains acidic and contaminated with significant levels of U(VI) and other radionuclides. Monitored Natural Attenuation (MNA) is a desired closure strategy for the site, based on the premise that regional flow of clean background groundwater will eventually neutralize the groundwater acidity, immobilizing U(VI) through adsorption. An in situ treatment system is currently in place to accelerate this in the downgradient portion of the plume and similar measures could be taken upgradient if necessary. Understanding the long-term pH and U(VI) adsorption behavior at the site is critical to assess feasibility of MNA along with the in-situ remediation treatments. This paper presents a reactive transport (RT) model and uncertainty quantification (UQ) analyses to explore key controls on the U(VI)-plume evolution and long-term mobility at this site. Two-dimensional numerical RT simulations are run including the saturated and unsaturated (vadose) zones, U(VI) and H+ adsorption (surface complexation) onto sediments...

Complexation of oppositely charged polyelectrolytes: effect of ion pair formation

Kudlay, Alexander; Ermoshkin, Alexander V.; de la Cruz, Monica Olvera
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 20/07/2004
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Complexation in symmetric solutions of oppositely charged polyelectrolytes is studied theoretically. We include polyion crosslinking due to formation of thermoreversible ionic pairs. The electrostatic free energy is calculated within the Random Phase Approximation taking into account the structure of thermoreversible polyion clusters. The degree of ion association is obtained self-consistently from a modified law of mass action, which includes long-range electrostatic contributions. We analyze the relative importance of the three complexation driving forces: long-range electrostatics, ion association and van der Waals attraction. The conditions on the parameters of the system that ensure stability of the complex with addition of salt are determined.

Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation

Vitorazi, L.; Ould-Moussa, N.; Sekar, S.; Fresnais, J.; Loh, W.; Chapel, J. -P.; Berret, J. -F.
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 02/10/2014
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Recent studies have pointed the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain to be answered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of sizes 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Beyond, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.; Comment: 25 pages including Supporting Information to appear in Soft Matter

Formation of Two 1:1 Chlorogenic Acid: β-cyclodextrin Complexes at pH 5: Spectroscopic, Thermodynamic and Voltammetric study

Álvarez-Parrilla,Emilio; Palos,Ricardo; Rosa,Laura A. de la; Frontana-Uribe,Bernardo A.; González-Aguilar,Gustavo Adolfo; Machi,Lorena; Ayala-Zavala,Jesús Fernando
Fonte: Sociedad Química de México A.C. Publicador: Sociedad Química de México A.C.
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/06/2010 EN
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Complexation of chlorogenic acid (CA) by β-cyclodextrin (β-CD) at mildly acidic pH, was studied by fluorescence spectroscopy, isothermal titration calorimetry (ITC), cyclic voltammetry (CV) and NMR spectroscopy. Thermodynamic parameters (ΔH°, ΔS° and K) determined by both fluorescence and ITC, showed that the complexation of CA by β-CD is an enthalpy-driven process. Results show that CA molecule can be complexed through both polyphenolic and quinic acid moiety, leading to the formation of two supramolecular isomers with 1:1 stoichiometry.