Search results for "Protonation"
showing 10 items of 583 documents
Supramolecular interactions of hexacyanocobaltate(III) with polyamine receptors containing a terminal anthracene sensor
2003
Abstract The fluorescence emission properties of a series of chemosensors containing a polyamine receptor bearing an anthracene signaling unit were studied. The fluorescence emission intensity is dependent on the protonation degree of the receptor, the fully protonated form exhibiting the highest emission intensity. By removing protons from the nitrogens a quenching effect can be observed, due to an electron-transfer from the amine to the excited fluorophore. The rate constant of the quenching process is exponentially dependent on the distance of the nitrogen from which the electron is transferred (β=0.6 A−1). The ability of the chemosensors for signaling anions was tested through the model…
Potentiometric, NMR, and Fluorescence-Emission Studies on the Binding of Adenosine 5′-Triphosphate (ATP) by Open-Chain Polyamine Receptors Containing…
2003
The interaction in aqueous solution of adenosine 5′-triphosphate (ATP) with a series of open-chain polyamines linked at one or both ends to anthrylmethyl or naphthylmethyl fragments was followed by potentiometric titration, 1H-, 13C-, and 31P-NMR spectroscopy, and by steady-state fluorescence measurements. The results revealed greater stabilities for the compounds containing one anthracene moiety than for those with one naphthalene moiety, the stabilities of the compounds with both ends N-substituted with naphthylmethyl groups being close to those containing just one anthrylmethyl unit. The 1H-NMR spectra showed that in all systems, there is involvement of π-π stacking interactions in the s…
Thermodynamic and fluorescence emission studies on chemosensors containing anthracene fluorophores. Crystal structure of {[CuL1Cl]Cl}2·2H2O [L1 = N-(…
1999
The co-ordination capabilities toward hydrogen ions, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ of the novel receptor 2,6,9,13-tetraaza[14](9,10)anthracenophane (L) and of its open-chain counterpart N-(3-aminopropyl)-N′-3-(anthracen-9-ylmethyl)aminopropylethane-1,2-diamine (L1) is described. Stepwise protonation constants of the cyclic receptor (L) are lower than those of the open-chain receptor (L1) . Quenching effects of the fluorescence emission occur upon first and second deprotonation of L and upon second deprotonation of L1. Stability constants of the Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ complexes follow the Irving–Williams trend and are intermediate between those of triethylenetetraamine with termin…
Switching from intramolecular energy transfer to intramolecular electron transfer by the action of pH and Zn2+ co-ordination
2002
Abstract Intramolecular electron (eT) and energy transfer (ET) have shown to occur in a covalently linked donor–acceptor (CLDA) system consisting of a naphthalene donor covalently linked through a polyamine chain connector to an anthracene acceptor; the connector has been chosen in order to switch ON or OFF the energy flux as a function of its protonation state as well as by co-ordination to Zn 2+ . The largest energy transfer efficiency ( η =0.61) occurs for the fully protonated form (pH 9 (eT) from the lone pairs of the nitrogens to the excited fluorophore takes place, leading to complete quenching of the emission. On the other hand at neutral and basic pH values, co-ordination of Zn 2+ p…
Improved Efficacy of Synthesizing *MIII-Labeled DOTA Complexes in Binary Mixtures of Water and Organic Solvents. A Combined Radio- and Physicochemica…
2018
Typically, the synthesis of radiometal-based radiopharmaceuticals is performed in buffered aqueous solutions. We found that the presence of organic solvents like ethanol increased the radiolabeling yields of [68Ga]Ga-DOTA (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacatic acid). In the present study, the effect of organic cosolvents [ethanol (EtOH), isopropyl alcohol, and acetonitrile] on the radiolabeling yields of the macrocyclic chelator DOTA with several trivalent radiometals (gallium-68, scandium-44, and lutetium-177) was systematically investigated. Various binary water (H2O)/organic solvent mixtures allowed the radiolabeling of DOTA at a significantly lower temperature than …
Polyamine Linear Chains Bearing Two Identical Terminal Aromatic Units. Evidence for a Photo Induced Bending Movement
2001
Abstract Several chemosensors bearing a fluorescent unit at both ends of a linear polyamine chain were synthesised. The protonation as well as the association constants with Cu2+ and Zn2+ were determined by potentiometry in 0.15 mol dm−3 NaCl at 298.1 K. In the case of 1,16-bis(1-naphthylmethyl)-1,4,7,10,13,16-hexaazadecane hexahydrochloride (L1), formation of an excimer emission in aqueous acidic solutions was observed. The system was characterized by steady state fluorescence emission and by time resolved fluorescence. In the ground state the molecule is expected to adopt a more or less linear conformation, while in the excited state a bending movement of the chain must occur in order to …
Water and oxoanion encapsulation chemistry in a 1H-pyrazole azacryptand
2019
Anion complexes of the cryptand built with the tripodal amine tris(2-aminoethyl)amine, known as tren, with water and several oxoanions of biological and environmental interest (nitrate, sulfate, phosphate, perchlorate and arsenate) have been crystallized from aqueous solution and resolved with single-crystal X-ray diffraction. All crystals show guest species encapsulated in the interior of the cavity as well as, in some cases, sitting in the grooves defined by the arms of the macrocycle. Hydrogen bonding and electrostatic interactions play a major role in anion binding to the host. The macrocycle is able to encapsulate anions in a wide range of protonation degrees. Solution studies have bee…
Synthesis, solid state and solution studies of cobalt(II) complexes with 2-hydroxyiminopropanoic acid
2013
Abstract This paper describes the synthesis of the Zn(II) complex with H2L = 2-hydroxyiminopropanoic acid. The final structure incorporated two linear dimeric anions with two Zn2+ atoms, which are linked by a carbonate anion into a tetranuclear unit. In each dinuclear unit, the two Zn(II) ions are coordinated by three molecules of the doubly deprotonated ligand in two different coordination modes. This result is confirmed both by X-ray crystallography and by ESI-MS investigations of the crystals dissolved in water. Equilibrium studies of the zinc(II) complexes formed by H2L in aqueous solution based on independent pH-metric titrations and zinc ion-selective electrode (ISE) titrations indica…
A study of dimethyltin(IV)-L-cysteinate in aqueous solution
1988
The in vivo activity of some R2Sn-L-cysteinate complexes (R = Me, Et, n-Bu) against murine P-388 leukaemia has been tested. Only the Et2Sn(IV) complex showed a marginal positive effect. Trigonal bipyramidal tin environments with two carbon (R) atoms and the sulfur atom in the equatorial plane and oxygen (carboxylate) and nitrogen (NH2) in apical positions have been proposed for the solid compexes (R = Me, Et, n-Bu, Ph) on the basis of experimental Mossbauer parameters and infrared (IR) data. Aqueous solutions of the Me2SnL-cysteinate have been studied by IR, 1H NMR and 119Sn Mossbauer spectroscopy (in frozen solution) at different pH values to identify the Me2Sn(IV) species present. At pH >…
Speciation of Organic Matter in Natural Waters-interaction of polyacrylates and polymethacrylates with major cation components of seawater
2004
Abstract The speciation of some high molecular weight polycarboxylates was studied in different ionic media. Polyacrylates here investigated ( W =2.0, 5.1 and 20.0 kDa) form weak species with alkali metal cations ( K =10 2 mol l −1 , t =25 °C, I =0 mol l −1 ) and quite stable complexes with alkaline earth metal cations ( K >10 6 mol l −1 , t =25 °C, I =0 mol l −1 ). Results are reported from experiments performed in a multicomponent electrolyte solution simulating the major composition of seawater (artificial seawater). Protonation constants in this medium are expressed as a polynomial function of S 1/2 ( S =salinity) and the sharp lowering with respect to values obtained in non-interacting…