Thermodynamics of sulfate anion binding by macrocyclic polyammonium receptors

The interaction of SO42− with polyammonium cations derived from fourteen polyamines (5 polyazacycloalkanes, 2 polyazacyclophanes, 3 phenanthrolinacyclophanes, 2 dibenzenacyclophanes and 2 acyclic polyamines) in aqueous solution has been studied by means of potentiometric and microcalorimetric techniques. Only 1 : 1 receptor–anion complexes have been found in solution. Complexed species of considerable stability are formed, although the two acyclic polyamines (dimethylpentaethylenehexaamine and dimethylhexaethyleneheptaamine) and the smallest phenanthrolinacyclophane do not interact with the anion. The complexation reactions are endothermic, or almost athermic, and promoted by invariably fav…

A simple helical macrocyclic polyazapyridinophane as a stereoselective receptor of biologically important dicarboxylates under physiological conditions.

The interaction of a synthetic enantiopure azamacrocyclic receptor (L) with biologically important chiral dicarboxylates (A, 1-7) has been studied by means of potentiometric titrations in 0.15 M NaCl aqueous solution in a wide pH range. This macrocycle forms strong complexes of the type [HnLA](n-2) (with n = 0-5). As a general trend, the binding is much tighter at basic or neutral pH than in acidic medium. Interestingly, nonprotected excitatory amino acids (Asp and Glu) are strongly bound even at acidic pH. Regarding selectivity, the receptor showed stereoselective binding toward those substrates bearing an H-bonding donor at Calpha, being S-selective in most of the cases, except for glutam…

Switching from intramolecular energy transfer to intramolecular electron transfer by the action of pH and Zn2+ co-ordination

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…

Naphthalene-containing polyamines supported in nanosized boehmite particles

Boehmite nanoparticles with covalently linked polyamine chains functionalized with naphthalene fluorophores have been prepared and characterized. The characterization of the materials by elemental microanalysis, X-ray powder diffraction, MAS 29Si NMR and electron microscopy unambiguously prove that the covalent anchorage had occurred. Steady-state fluorescence emission studies show that the luminescent properties of the modified nanoparticles are sensitive to changes in concentration of hydrogen ions, metal ions and anionic nucleotides such as ATP. The behaviour of the attached materials in aqueous solution is parallel to the behaviour of the single fluorophoric polyamines. Comparisons are …

Thermodynamic and kinetic studies on the Cu2+ coordination chemistry of a novel binucleating pyridinophane ligandElectronic supplementary information (ESI) available: Table S1: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with ligand L. Table S2: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with macrocycle L1. Fig. S1: Variation of some selected 13C chemical shifts as a function of pH. See http://www.rsc.org/suppdata/dt/b2/b209013a/

The synthesis and coordination chemistry of the novel pyridine-functionalized ligand 2,6,9,12,16-pentaaza[17]-(2,6)pyridinophane (L1) is described. The compound behaves as a hexaprotic base in aqueous solution. NMR studies indicate a protonation pattern in which the sp2 pyridine nitrogen (N(py)) does not undergo a net protonation although it is involved in formation of hydrogen bonds. L1 forms mono and binuclear hydroxylated complexes. The crystal structure of [CuL1](ClO4)2 shows a square planar coordination for Cu2+ with the pyridine and the three central nitrogens of the chain forming the vertices of the square. The benzylic nitrogens could be occupying the axial positions of a strongly a…

Solid-State Electrochemical Method for Determining Core and Shell Size in Pd@PdO Nanoparticles

Electrochemical characterization of palladium nanoparticles surrounded by a palladium oxide shell (Pd@PdO) is described from a combination of voltammetry plus electrochemical quartz crystal microbalance experiments at nanoparticle deposits on graphite electrodes in contact with aqueous H2SO4 and NaOH solutions. A method for determining the metal core size and oxide shell thickness of the Pd@PdO nanoparticles, based on a combination of conventional voltammetry of nanoparticles in DMSO solution and voltammetry of nanoparticle deposits in contact with 0.10 M aqueous NaOH solution, is described.

A polyazacyclophane containing two biphenyl subunits as a versatile cation and anion receptor

Abstract The synthesis, protonation behaviour and coordination capabilities towards Cu 2+ , Zn 2+ and towards the nucleotides ATP and ADP of a cyclophane ditopic receptor 2,6,10,23,27,31-hexaaza[11,11](2,2′)biphenylophane containing two 2,2′-biphenylene spacers linked to the ends of 1,5,9-triazanonane chains are presented.

The Professional Profile of Intergenerational Program Managers: General and Specific Characteristics

The interest around intergenerational programs and the fostering of intergenerational relationships is growing internationally. However, studies on the profile and functions of intergenerational program managers are still scarce. Furthermore, available approaches to the traits and functions of intergenerational program managers have not highlighted which features are distinctive of these professionals. Through a Delphi study undertaken in Spain, with participation of 18 intergenerational program managers and 12 intergenerational specialists, consensus was reached around characteristics of both the general profile of intergenerational program managers and the specificities of this occupation…

New molecular catalysts for ATP cleavage. Criteria of size complementarity

The interaction of the cyclophane receptor 2,5,8,11,14,17-hexaaza[18]metacyclophane (L) with the nucleotides ATP, ADP and AMP is described. L yields one of the largest rate enhancements for hydrolytic ATP cleavage observed in macrocyclic polyamines. The process is specific for the formation of ADP and involves a high degree of geometrical complementarity between host and guest species. The analogue compound 24-hydroxy-2,5,8,11,14,17-hexaaza[18]metacyclophane (L11) shows also a high degree of ATP activation. However, in this case deprotonation of the hydroxy group results in almost complete quenching of the ATPase activity above pH 7.0.

Cation and anion recognition characteristics of open-chain polyamines containing ethylenic and propylenic chains

Abstract The interaction of the polyamines 4,7,10,13-tetraazahexadecane-1,16-diamine (L1) and 4,7,10-triazatridecane-1,13-diamine (L2) with H + , Cu 2+ , Zn 2+ , Co 2+ and the nucleotides ATP, ADP and AMP has been followed by NMR and potentiometric studies performed at 298.1 K in 0.15 mol dm −3 NaClO 4 . The influence of the different sequences of hydrocarbon chains and chelate rings present in the ligands on the values of the protonation constants, the stability of the metal ion complexes as well as in the co-ordination to nucleotides is analysed. The formation of mixed complexes has been investigated for the system Cu 2+ –L1–AMP.

Switching from intramolecular energy transfer to intramolecular electron transfer by the action of pH and Zn2+ co-ordination

http://www.sciencedirect.com/science/article/B6TFN-44SKJK4-4/1/7cd5958d3acd1757d2b3a88517f1d557

Anion coordination chemistry in aqueous solution of polyammonium receptors

The behavior of polyamines as receptors of selected families of anions in water is explored. First metallocyanide interaction with saturated polyammonium hosts is analyzed both in solution and in the solid state. The utility of potentiometry, multinuclear NMR, microcalorimetry and cyclic voltammetry to describe solution features of this chemistry is described for selected systems. Sulfate, phosphate, polyphosphate and nucleotide interactions with large polyammonium receptors are then reviewed. Hydrogen bond formation is discussed from a thermodynamic point of view. The influence of the presence of aromatic fragments within the structure on the binding strength is discussed. Factors affectin…

A highly enantioselective abiotic receptor for malate dianion in aqueous solution

The highly enantioselective molecular recognition of the malate dianion by a synthetic receptor in aqueous solution has been studied by potentiometric titrations, mass spectrometry (ESI-MS), diffusion measurements (PGSE NMR) and molecular modeling. Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es

Potentiometric, NMR, and Fluorescence-Emission Studies on the Binding of Adenosine 5′-Triphosphate (ATP) by Open-Chain Polyamine Receptors Containing Naphthylmethyl and/or Anthrylmethyl Groups

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…

Ground and excited state properties of polyamine chains bearing two terminal naphthalene units

A series of compounds bearing two naphthalene units linked through methylene groups to both ends of different open-chain polyamines has been investigated. The fluorescence emission studies show the presence of an excimer species whose formation depends on the protonation state and length of the polyamine chains and implies the existence of a bending movement in the excited state allowing the two naphthalene units to approach and interact. This interpretation was clearly proven by time-resolved fluorescence with the appearance of double exponential decays with a rise time observed at the excimer emission wavelength. For comparison purposes one bis-chromophoric compound containing a rigid cha…

A Ferromagnetic [Cu3(OH)2]4+Cluster Formed inside a Tritopic Nonaazapyridinophane: Crystal Structure and Solution Studies

Copper(ii) and Zn(ii) coordination chemistry of tetraaza[n]cyclophanes

The acid–base behaviour and Zn2+ and Cu2+ metal coordination chemistry of the novel orthocyclophane ligands 2,5,8,11-tetraaza[12]orthocyclophane (L2) and 2,5,9,12-tetraaza[13]orthocyclophane (L3) and metacyclophane 2,5,8,11-tetraaza[12]metacylophane (L1) are studied. Important differences in the chemistry of these compounds are found depending on the substitution of the aromatic ring. The ortho derivatives are much more basic in their first two protonation steps while the metacyclophane presents much larger constants in the third and fourth protonation stages. The crystal structure of the picrate salt of [H2L3]2+ shows an alternate disposition of the protons in the molecule with formation o…

Amplitud de distribución eritrocitaria y riesgo de mortalidad en pacientes con insuficiencia cardiaca aguda

Resumen Fundamento y objetivo El ancho de distribucion eritrocitaria (ADE) es una medida cuantitativa de la variabilidad del tamano de los eritrocitos circulantes utilizada clasicamente para el diagnostico diferencial de las anemias. En los ultimos anos, se ha sugerido que el ADE podria ser un marcador pronostico util en pacientes con insuficiencia cardiaca cronica. Sin embargo, es escasa la evidencia que respalda su papel en poblacion no seleccionada con insuficiencia cardiaca aguda (ICA), de manera independiente a los factores de riesgo establecidos. El objetivo del estudio fue establecer la asociacion entre el ADE y la mortalidad a largo plazo en pacientes ingresados por ICA. Pacientes y…

Polyamines containing naphthyl groups as pH-regulated molecular machines driven by light

A series of compounds made up by linking methylnaphthalene fragments at both ends of different polyamine chains have shown to behave as pH-regulated molecular machines driven by light and fluorescence emission studies have proved the formation of an excimer between the two naphthalene units whose appearance, fluorescence intensity and decay times depend on the pH value of the media. Albelda Gimeno, Maria Teresa, Teresa.Albelda@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es ; Soriano Soto, Concepción, Concepcion.Soriano@uv.es