Phenylenedioxydiacetamide—End group effect

A series of neutral ligands featuring ether and amide groups were prepared. The complexation studies suggest a strong participation of the extra terminal amide group.Taken in part from the Master's Thesis of Antonio Paulo Altoé, Instituto Militar de Engenharia, Rio de Janeiro, Brasil (1979).     

Voltammetry and EQCM Investigation of Glutathione Monolayer and Its Complexation with Cu2+

The glutathione (GSH) self‐assembled monolayer and its compexlation with Cu²⁺ were studied by using voltammetry and EQCM. It was found that the monolayer could rearrange during the redox process of Cu²⁺/Cu⁺. The protonating, or not, of the carboxyl terminates of the adsorpted GSH molecules influence the compexlation interaction significantly for they are the key binding sites. The GSH monolayer had the capacity to accumulate Cu²⁺ and the monolayer modified gold electrode was employed to detect the low levels of Cu²⁺ with a limit of 1.0×10^?10 mol L^?1.     

Interactions of ligands with lithium picrate in dioxane

The interaction of several cyclic ethers, poly(ethylene glycol dimethyl ether)s, nitriles, esters and ketones with lithium picrate in dioxane at 25°C was investigated by means of a competition method using cross-linked poly(ethylene oxide) (PEO) as the insoluble ligand. The Langmuir-Klotz isotherm of LiPi binding to the PEO gel gave an apparent binding constant, K, as a function of the concentration of added ligand. Plots of 1/K vs. the ligand concentration then yielded the formation constant, K _L , of the ligand complex with LiPi. The results demonstrate that in dioxane one ligand molecule binds to LiPi. While there is some dependence on the Gutmann donicity number of the respective ligands, steric factors often play a dominant role in determining the value of K _L . The results were compared with complexation data obtained on similar systems but by different methods.     

Investigation of the complexation reaction between 2-diethylaminomethyl-4-methylphenol and ZnCl2. Reaction mechanism and solvent effects

The reaction mechanism of the chemical reaction of 2-diethylaminomethyl-4-methylphenolate with ZnCl₂ is investigated by means of the PM3 semi-empirical method. We propose two different but competitive stepwise pathways going from the isolated reactants to the tetra-coordinated bidentate final complex, where the zinc atom is bonded both to the oxygen and to the nitrogen atom of the ligand. Each pathway proceeds via different monodentate intermediate complexes. This study shows that either the first chemical bond formed between ZnCl₂ and 2-diethylaminomethyl-4-methylphenolate is the Zn–O bond or the Zn–N bond. The direct pathway going from the reactants to the final product through a concerted asynchronous mechanism is found to be unrealistic, since it involves a second order saddle point.

Solvent effects are taken into account with the SCRF dielectric continuum model at the PM3 and (RHF/3-21G) levels of theory. This preliminary study shows that the complex formation is favored by the use of polar solvent.     

Complexation behaviour of radiation synthesized poly(vinylbenzyltrimethylammonium chloride) and its gel with potassium hexacyanoferrates (II, III) and potassium persulfate in aqueous medium

High energy gamma radiation has been used to synthesize linear poly(vinylbenzyltrimethylammonium chloride) (PVBT) as well as crosslinked PVBT gels. Complexation behaviour of linear and crosslinked PVBT with K₂S₂O₈, K₃[Fe(CN)₆] and K₄[Fe(CN)₆] have been studied by viscometry, turbidity and equilibrium swelling measurements. The stoichiometry of the complex formed was found to be a function of charge on the anions of complexing species. Crosslinked poly(vinylbenzyltrimethylammonium chloride) gels were found to desorb some of the embedded water when swollen gels were placed in these salt solutions. Existence of strong ionic interactions between polymer chains and complexing salts was confirmed by changes in equilibrium swelling of complexed crosslinked matrices as well as in the stoichiometry of linear PVBT complexes in presence of strong electrolytes like NaCl.     

The Hydrolysis of Hydroxamic Acid Complexants in the Presence of Non-oxidizing Metal Ions 1: Ferric Ions

Hydroxamic acids (XHAs) are organic compounds with affinities for cations such as Fe³⁺, Np⁴⁺ and Pu⁴⁺ and have been identified as useful reagents in nuclear fuel reprocessing. Acid catalyzed hydrolysis of free XHAs is well known and may impact negatively on reprocessing applications. The hydrolysis of metal-bound XHAs within metal ion-XHA complexes is less understood. With the aid of speciation diagrams, we have modelled UV-visible spectrophotometric kinetic studies of the acid-catalyzed hydrolysis of acetohydroxamic acid (AHA) bound to the model ion Fe(III). These studies have yielded the following information for the hydrolysis of AHA in the Fe(AHA)²⁺ complex at 293 K: (i) the order with respect to [H⁺] during the rate determining step, m=0.97, is the same as for the free ligand, indicating a similarity of mechanisms; and (ii) the kinetic rate parameter, k ₁=1.02×10⁻⁴ dm³⋅mol⁻¹⋅s⁻¹, is greater than that for the free ligand, k ₀=1.84×10⁻⁵ dm³⋅mol⁻¹⋅s⁻¹ for pH>−0.5, a result that is consistent with a Hammett analysis of the system.     

Thermally activated and light-induced metal ion complexation of 5′-(hydroxy)spiroindolinonaphthooxazines in polar solvents

Chelation with Al(III), Fe(II) or Cu(II) of the open photomerocyanine form obtained under steady irradiation of spiroindolinonaphthooxazines, with a hydroxyl group at the 5′ position in the naphthooxazine moiety, induces a slight hypsochromic shift of its visible absorption band and increases the lifetime of this form, slowing down its thermal bleaching in the dark (rate constant  10⁻³ s⁻¹). Complexation with Al(III), Fe(II) or Cu(II) allows the spiroindolinonaphthooxazines to isomerize to their open coloured form even under dark conditions giving a complex spectroscopically identical to the photoinduced product. The activation energy of thermal complexation is independent of the metal ion which implies the ring opening as the rate determining step.     

Alternatives for the reduction of Cu(II) ion levels in hemodialysis membranes produced from sugar-cane bagasse

The objective of the present study was to seek alternatives for the reduction of Cu(II) ion levels in hemodialysis membranes produced by the cuprammonium process. The alternatives used were: (a) replacement of the solvent Cu(NH₃)₄(OH)₂, used in the original process, with Cu(EDA)₂(OH)₂, and (b) increasing the reflux time of the bagasse purification process from 1.5 to 3.0 h. The experimental results were obtained by analysis of Cu(II) content in the membranes by atomic absorption, by complexometry via UV/Vis spectroscopy of the solutions of filter paper, bagasse and lignin, and by monitoring the various stages of the purification process (by FTIR and by loss of mass), i.e. pretreatment with 0.25 M NaOH followed by treatment with 4.2 M EDA and reflux with EtOH/HNO₃ (20%, v/v). The results showed that the Cu(II) content in the membranes decreased with the use of the Cu(EDA)₂(OH)₂ solvent, that the purification process could not be improved further since cellulose degradation was observed, and that the Cu(II) content in the membranes produced was still to high for their use for hemodialysis treatment.     

Complexation between poly(N,N-diethylacrylamide) and poly(acrylic acid) in aqueous solution

The complexation between poly(N,N-diethylacrylamide) (PDEA) and poly(acrylic acid) (PAA) in aqueous solution was studied by viscometric, potentiometric, and fluorescence techniques. It was found that an interpolymer complex formed between the two polymers through hydrogen bonding interactions with the stoichiometry of r=0.6 (r is unit molar ratio of PAA/PDEA), and the complex formation show the dependence on pH values. The phase behaviour studies showed that the lower critical solution temperature of the PDEA-PAA aqueous solution gradually increased with the increasing of r from 0.01 to 0.15, until a soluble system in the whole temperature region was obtained, which remained in the range of r=0.15-0.3. At higher PAA concentrations, when r is above 0.3, the system appeared phase separation, and almost no temperature dependence was observed. Based on these conclusion and structure characteristics of PDEA and PAA, a model containing only short sequences of monomer residues was proposed for the structure of PDEA-PAA complex.     

Solubility, dissociation and complexation with Nd(III) and Th(IV) of oxine, thenoyltrifluoroacetone and 1,10-phenanthroline in 5.0 m NaCl

Equilibria in the system of Nd(III) and Th(IV) with 8-hydroxyquinoline (oxine), thenoyltrifluoroacetone (HTTA) and 1,10-phenanthroline (phen) in 5.0 m NaCl solution have been investigated by spectroscopy and potentiometry. The solubility and deprotonation constants of the three organics were measured to be: pK_s = 3.09 ± 0.01, pK_a1 = 5.82 ±0.02, pK_a2= 10.00 ±0.01 for oxine; pK_s = 2.49 ± 0.01, pK_a1 = 6.47 ±0.03 for HTTA; pK_s = 2.86 ± 0.02, pK_a2 = 5.82 ± 0.05 for phen. The stabilities of the corresponding metal complexes are in the order M(oxine) > M(TTA) > M(phen), where M = Nd(III), Th(IV). For all three organic ligands, the Th(IV) complexation is stronger than that of Nd(III).