0000000001300238

AUTHOR

José M. Llinares

showing 44 related works from this author

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 …

Aqueous solutionChemistryExcited stateMoleculeProtonationGeneral ChemistryTime-resolved spectroscopyExcimerPhotochemistryGround stateFluorescenceSupramolecular Chemistry
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The size of aryl linker between two polyaza-cyclophane moieties controls the binding selectivity to ds-RNA vs ds-DNA

2013

Aryl-linked (pyridine- vs. phenanthroline-) bis-polyaza pyridinophane scorpiands PYPOD and PHENPOD strongly bind to the double stranded DNA and RNA, whereby very intriguing RNA over DNA selectivity is finely tuned by aryl-linker length and aromatic surface. Moreover, PYPOD and PHENPOD dimer formation at high compound/polynucleotide ratios is highly sensitive to the fine interplay between the steric and binding properties of compound-dimers and the DNA minor groove/RNA major groove. That is demonstrated by significantly different induced CD spectra, which allow spectroscopic differentiation between various DNA/RNA secondary structures. A significantly higher (micromolar) antiproliferative ef…

Aza CompoundsBinding SitesMolecular StructureStereochemistryChemistryPyridinesDimerOrganic ChemistryRNADNABiochemistrypolyaza-cyclophane ; DNA ; RNA ; selectivity ; antiproliferative activitychemistry.chemical_compoundPolynucleotidePhysical and Theoretical ChemistryBinding siteParticle SizeLinkerBinding selectivityDNACyclophanePhenanthrolinesRNA Double-Stranded
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Cryptand-like anion receptors

2010

The design of supramolecular hosts for anions began with simple diaza bicycles, named katapinands, and has evolved over the last 40 years to a number of elegantly designed receptors capable of binding many different anions. About the same time the term cryptand appeared in reference to another bicyclic compound that was selective for alkaline-earth ions. Since the first report these simple bicycles, a vast arena of hosts has appeared, including acyclic, monocyclic, and other multicyclic supramolecular receptors. Studies of these systems have revealed considerable information about anion coordination chemistry, including the fact that many of these complexes mimic their transition-metal coro…

chemistry.chemical_classificationBicyclic moleculeCovalent bondChemistryStereochemistryCoordination numberCryptandSupramolecular chemistryGeneral ChemistryIonCoordination complexChemical Society Reviews
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A step forward in the development of superoxide dismutase mimetic nanozymes: the effect of the charge of the surface on antioxidant activity

2019

Two binucleating hezaaza macrocycles containing a pyridinol spacer have been prepared and characterised. Protonation studies indicate the deprotonation of the phenol group at relatively low pH values with the concomitant occurrence of a keto-enolic equilibrium. These ligands readily form binuclear Cu2+ and Zn2+ complexes as denoted by potentiometric and spectroscopic studies. The binding of the metals yields to the ready deprotonation of the phenol with the stabilisation of the keto form that results in complexes of greater stabilities than the analogous ones containing pyridine as spacer instead of pyridine. Mixed Cu2+–Zn2+-complexes were also detected in aqueous solutions containing equim…

inorganic chemicalsAqueous solutionbiologyChemistryGeneral Chemical EngineeringPotentiometric titrationchemistry.chemical_elementProtonation02 engineering and technologyGeneral Chemistry010402 general chemistry021001 nanoscience & nanotechnology01 natural sciencesMedicinal chemistryCopper0104 chemical sciencesSuperoxide dismutasechemistry.chemical_compoundDeprotonationPyridinebiology.proteinPhenol0210 nano-technologyRSC Advances
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Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu2+metal ions within polytopic receptors

2013

Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out. Complex formation occurs with polyphasic kinetics for both receptors, although a significant difference is found between bot…

Hydrogen bondChemistryMetal ions in aqueous solutionPotentiometric titrationKineticsAnalytical chemistryDecompositionInorganic ChemistryMetalCrystallographyReaction rate constantvisual_artvisual_art.visual_art_mediumProton NMR
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Fluoride Ion Receptors: A Comparison of a Polyammonium Monocycle Versus its Bicyclic Corollary

2001

Two polyammonium macrocyclic receptors, the monocyclic 3,6,9,17,20,23-hexaazatricyclo [23.3.1.111,15]triaconta-1(29), 11,13,15(30),25,27-hexaene (L1) and its bicyclic analog 1,4,12,15,18,26,31,39-o...

chemistry.chemical_compoundCorollaryBicyclic moleculeChemistryStereochemistryGeneral ChemistryCrystal structureReceptorFluorideIonSupramolecular Chemistry
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N-(2-methyl-indol-1H-5-yl)-1-naphthalenesulfonamide : a novel reversible antimitotic agent inhibiting cancer cell motility

2016

Este es el post-print que se ha publicado de forma definitiva en: https://www.sciencedirect.com/science/article/abs/pii/S0006295216301423 A series of compounds containing the sulfonamide scaffold were synthesized and screened for their in vitro anticancer activity against a representative panel of human cancer cell lines, leading to the identification of N-(2-methyl-1H-indol-5-yl)-1-naphthalenesulfonamide (8e) as a compound showing a remarkable activity across the panel, with IC50 values in the nanomolar-to-low micromolar range. Cell cycle distribution analysis revealed that 8e promoted a severe G2/M arrest, which was followed by cellular senescence as indicated by the detection of senescen…

0301 basic medicineIndolesSulfonamides - Therapeutic use.MotilityApoptosisAntimitotic AgentsMicrotubulesBiochemistryJurkat Cells03 medical and health sciences0302 clinical medicineCell MovementTubulinMicrotubuleCélulas cancerosas - Motilidad.Apoptosis.HumansSulfamidas - Uso terapéutico.MitosisCell ProliferationPharmacologySulfonamidesMolecular StructurebiologyCancer cells - Motility.Cell cycleCell biologyMitosis.030104 developmental biologyTubulinCell cultureApoptosis030220 oncology & carcinogenesisCancer cellMCF-7 Cellsbiology.proteinDrug Screening Assays AntitumorDNA Damage
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Acid–base properties of functionalised tripodal polyamines and their interaction with nucleotides and nucleic acids

2010

Novel, highly positively charged tripodal polyamines with appended heterocyclic moieties revealed an intriguing panel of protonation species within the biologically relevant range. Studied compounds bind nucleotide monophosphates by mostly electrostatic interactions but only the imidazole analogue showed selectivity toward UMP in respect to other nucleotides. Strong binding of all the studied compounds to both ds-DNA and ds-RNA is to some extent selective toward the latter, showing rather rare RNA over DNA preference.

tripodal polyamines; DNA and RNA interactions; RNA selectivity; nucleotidesMagnetic Resonance SpectroscopyStereochemistryProtonation010402 general chemistry01 natural sciencesBiochemistrychemistry.chemical_compoundNucleic AcidsPolyaminesImidazoleNucleotidePhysical and Theoretical Chemistrychemistry.chemical_classificationMolecular StructureNucleotides010405 organic chemistryOrganic ChemistryWaterRNANuclear magnetic resonance spectroscopyHydrogen-Ion Concentration0104 chemical sciencesSolutionsChemistrychemistryNucleic acidThermodynamicsProtonsSelectivityDNAOrganic & Biomolecular Chemistry
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Intermolecular binding modes in a novel [1 + 1] condensation 1H-pyrazole azamacrocycle: a solution and solid state study with evidence for CO2 fixati…

2013

The synthesis of a novel cyclophane (L1) consisting of a 1H-pyrazole moiety linked through methylene groups to a 1,5,9,13-tetraazadecane chain is described. As far as we know, this is one of the first reported syntheses of a [1 + 1] condensation 1H-pyrazole azamacrocyclic ligand. The crystal structures of the complexes [Cu2(H(H(-1)L1))(H(-1)L1)](ClO4)3·3.75H2O (1) and ([Cu2(H(H(-1)L1))(0.5)(H(-1)L1)(1.5)]2(ClO4)3Br2·4.2H2O (2) show that Cu(2+) coordination leads to formation of 2:2 Cu(2+):L dinuclear dimeric complexes in which the 1H-pyrazole units lose a proton behaving as bis(monodentate) bridging ligands. Unlike previously reported complexes of [2 + 2] pyrazole azamacrocycles, the pyrazo…

Models MolecularAza CompoundsDenticityMacrocyclic CompoundsStereochemistryLigandCrystal structurePyrazoleCarbon DioxideCrystallography X-RayInorganic Chemistrychemistry.chemical_compoundCrystallographychemistryCoordination ComplexesPyridineMoietyPyrazolesPhysical and Theoretical ChemistryMethyleneCyclophaneInorganic chemistry
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Toward a Rational Design of Polyamine-Based Zinc-Chelating Agents for Cancer Therapies.

2020

In vitro viability assays against a representative panel of human cancer cell lines revealed that polyamines L1a and L5a displayed remarkable activity with IC50 values in the micromolar range. Preliminary research indicated that both compounds promoted G1 cell cycle arrest followed by cellular senescence and apoptosis. The induction of apoptotic cell death involved loss of mitochondrial outer membrane permeability and activation of caspases 3/7. Interestingly, L1a and L5a failed to activate cellular DNA damage response. The high intracellular zinc-chelating capacity of both compounds, deduced from the metal-specific Zinquin assay and ZnL2+ stability constant values in solution, strongly sup…

Antineoplastic AgentsApoptosis01 natural sciences03 medical and health scienceschemistry.chemical_compoundStructure-Activity RelationshipCell Line TumorDrug DiscoveryPolyaminesHumansCytotoxicityCaspase030304 developmental biologyChelating Agents0303 health sciencesbiologyMolecular StructureChemistryRational designG1 Phase Cell Cycle Checkpoints0104 chemical sciencesCell biology010404 medicinal & biomolecular chemistryZincModels ChemicalApoptosisCell cultureDrug Designbiology.proteinMolecular MedicineQuantum TheoryDrug Screening Assays AntitumorPolyamineG1 phaseIntracellularJournal of medicinal chemistry
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Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism

2009

The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…

chemistry.chemical_classificationSpectrometry Mass Electrospray IonizationMolecular StructurePyridinesStereochemistryTripod (photography)ProtonationHydrogen-Ion ConcentrationLigandsKinetic energyAcid excesslaw.inventionCoordination complexInorganic Chemistrychemistry.chemical_compoundCrystallographyReaction rate constantchemistrylawPyridinePolyaminesProtonsPhysical and Theoretical ChemistryElectron paramagnetic resonanceCopperInorganic Chemistry
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Coordination Chemistry of Cu2+ Complexes of Small N-Alkylated Tetra-azacyclophanes with SOD Activity

2018

A new tetraaza-pyridinophane macrocycle (L1) N-alkylated with two isopropyl and one methyl groups symmetrically disposed has been prepared and its behavior compared with those of the unsubstituted pyridinophane (L3) and the related compound with three methyl groups (L2). The protonation studies show that, first, a proton binds to the central methylated amine group of L1, while, second protonation leads to a reorganization of the protons that are at this stage attached to the lateral isopropylated amines. The X-ray structure of [HL1]+ agrees with the UV–vis and NMR studies as well as with the results of DFT calculations. The stability of the Cu2+ complexes decreases on increasing the bulkine…

chemistry.chemical_classification010405 organic chemistryLigandProtonationCrystal structureAlkylation010402 general chemistry01 natural sciencesMedicinal chemistrySquare pyramidal molecular geometry0104 chemical sciencesCoordination complexInorganic ChemistrychemistryPhysical and Theoretical ChemistryIsopropylAlkylInorganic Chemistry
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Nitrate Encapsulation within the Cavity of Polyazapyridinophane. Considerations on Nitrate−Pyridine Interactions

2010

Interaction of nitrate anions with a cyclophane (L) containing two pyridine units connected to two diethylenetriamine bridges through methylene positions is reported both in pure water and in the solid state. The crystal structure of [H4L](NO3)4 shows that one of the nitrate anions resides in the macrocyclic cavity forming two sets of bifurcated hydrogen bonds with the four protonated amino groups of the macrocycle. This anion is symmetrically placed in the middle of the pyridine rings with distances between its nitrogen atom and the centroids of the ring of 3.58 A. Despite this location, calculations by theoretical analysis were carried out to confirm whether the stabilizing effect is due …

Hydrogen bondInorganic chemistryProtonationGeneral ChemistryCrystal structureCondensed Matter Physicschemistry.chemical_compoundCrystallographychemistryNitratePyridineDiethylenetriamineGeneral Materials ScienceMethyleneCyclophaneCrystal Growth & Design
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Synthesis and Cu(II) coordination of two new hexaamines containing alternated propylenic and ethylenic chains: Kinetic studies on pH-driven metal ion…

2006

Abstract The synthesis of the open-chain and cyclic polyamines, 1,5,8,12,15,19-hexaazaheptadecane (L1) and 2,6,9,13,16,20-hexaaza[21]-(2,6)-pyridinophane (L2), are described. The protonation constants and interaction constants with Cu(II) have been determined by potentiometric measurements carried out at 298.1 K in 0.15 mol dm −3 NaClO 4 . The values obtained are discussed as a function of the open-chain or cyclic nature of the ligands and compared with analogous polyamines containing different sets of hydrocarbon chains between the nitrogen donors. Kinetic studies on the acid-promoted dissociation of the Cu(II) complexes indicate that the mono and binuclear complexes of L1 decompose with d…

chemistry.chemical_classificationChemistryPotentiometric titrationKineticsInorganic chemistrychemistry.chemical_elementProtonationElectrochemistryNitrogenDissociation (chemistry)Inorganic ChemistryMetalCrystallographyHydrocarbonvisual_artMaterials Chemistryvisual_art.visual_art_mediumPhysical and Theoretical ChemistryInorganica Chimica Acta
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Equilibrium and Kinetic Properties of Cu II Cyclophane Complexes: The Effect of Changes in the Macrocyclic Cavity Caused by Changes in the Substituti…

2008

The o-B232, m-B232 and p-B232 cyclophanes result from attaching the terminal amine groups of 1,4,8,11-tetraazaundecane (232) to the benzylic carbons of the corresponding o-, m- or p-xylanes. The cavity size of these cyclophanes changes moderately as a consequence of the substitution at the aromatic ring. The effects caused by these changes on the equilibrium constants for protonation and CuII complex formation of the cyclophanes are analyzed and compared with those of the noncyclic 232 polyamine. All three cyclophanes form mononuclear complexes, but only o-B232 is able to coordinate to CuII through the four amine groups simultaneously, whereas m-B232 and p-B232 can only use three nitrogen d…

Inorganic ChemistrySteric effectschemistry.chemical_compoundCrystallographychemistryMetal ions in aqueous solutionKineticsAmine gas treatingProtonationPhotochemistryEquilibrium constantDissociation (chemistry)CyclophaneEuropean Journal of Inorganic Chemistry
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Luminescent supramolecular heterometallic macrocycles and their encapsulation on cholate gels

2018

The metal complex formed by coordination of Zn(II) to 1,7-bis(4-methylpyridine)-4-(2- naphthylmethyl)-1,4,7-triazaheptane (ZnL2+) was reacted in aqueous solution with [Pd(NO3)2(en)] and [Pt(NO3)2(en)] salts to form the self-assembled heterometallic macrocycles [Zn2L2Pd2(en)2]8+ and [Zn2L2Pt2(en)2]8+, respectively. Pd(II) and Pt(II)- coordination modulates the original emission of ZnL2+ arising from the presence of the naphthalene chromophore and the formation of the macrocycles can be monitored due to the PET process occurring with coordination of Pd(II) and Pt(II) to the pyridine units of ZnL2+. Additionally, several studies reveal that these heteromacrocycles can be encapsulated in Zn(II)…

LuminescenceGels (Farmàcia)ChemistrySupramolecular chemistryLuminescència02 engineering and technology010402 general chemistry021001 nanoscience & nanotechnology01 natural sciencesQuímica supramolecular0104 chemical sciencesEncapsulation (networking)Inorganic ChemistryChemical engineeringSelf-assembly0210 nano-technologyLuminescenceSupramolecular chemistryGels (Pharmacy)
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CO2 Fixation by Cu2+ and Zn2+ complexes of a terpyridinophane aza receptor. Crystal structures of Cu2+ complexes, pH-metric, spectroscopic, and elect…

2006

The synthesis of the terpyridinophane-type polyamine 2,6,9,12,16-pentaaza[17]-(5,5' ')-cyclo-(2,2':6',2' ')-terpyridinophane heptahydrobromide tetrahydrate (L.7HBr.4H2O) is described. L presents six protonation constants with values in the range 9.21-3.27 logarithmic units. L interacts with Cu2+ and Zn2+ forming in both cases, neutral, protonated, and hydroxylated mono- and binuclear complexes whose constants have been calculated by potentiometry in 0.15 M NaClO4 at 298.1 K. The crystal structures of the compounds [Cu(HL-carb)(H2O)](ClO4)3.2H2O (1) and [Cu2(H2L)(CO3)]2(ClO4)8.9H2O (2) have been solved by X-ray diffraction. In 1, the metal center presents square pyramidal geometry. The base …

StereochemistryProtonationCrystal structureElectrochemistryCrystallography X-RayInorganic ChemistryMetalchemistry.chemical_compoundPyridineElectrochemistryOrganometallic CompoundsPolyaminesMoleculePhysical and Theoretical ChemistryTetrahydrateMolecular StructureSpectrum AnalysisCarbon DioxideHydrogen-Ion ConcentrationPlantsSquare pyramidal molecular geometryCrystallographyZincchemistryvisual_artvisual_art.visual_art_mediumCopperInorganic chemistry
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Effect of Nitrogen Methylation on Cation and Anion Coordination by Hexa- and Heptaazamacrocycles. Catalytic Properties of These Ligands in ATP Dephos…

1996

The stability constants of the complexes formed by 1,10-dimethyl-1,4,7,10,13,16-hexaazacyclooctadecane (L) and 1,4,7-trimethyl-1,4,7,10,13,16,19-heptaazacyclohenicosane (L1) with Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+), as well as that for the formation of PbL2(2+) (L2 = 1,4,7,13-tetramethyl-1,4,7,10,13,16-hexaazacyclooctadecane), were determined by means of potentiometric (pH-metric) titrations in 0.15 mol dm(-)(3) NaClO(4) at 298.1 +/- 0.1 K. The enthalpy changes for the formation of Cu(2+) complexes with L and L1 were measured by means of microcalorimetry. These thermodynamic data were compared with those previously reported for L2, 1,4,7,10,13,16-hexaazacyclooctadecane (L3), and 1,4,…

Isothermal microcalorimetryChemistryPotentiometric titrationInorganic chemistryNuclear magnetic resonance spectroscopyHEXAMedicinal chemistryCatalysisInorganic ChemistryMetalDephosphorylationvisual_artvisual_art.visual_art_mediumTitrationPhysical and Theoretical Chemistry
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Anion coordination chemistry in aqueous solution of polyammonium receptors

2006

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…

chemistry.chemical_classificationIsothermal microcalorimetryAqueous solutionHydrogen bondPolyphosphateInorganic chemistryCombinatorial chemistryCoordination complexInorganic ChemistryMetalchemistry.chemical_compoundchemistryvisual_artMaterials Chemistryvisual_art.visual_art_mediumNucleotidePhysical and Theoretical ChemistryCyclic voltammetryCoordination Chemistry Reviews
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Synthesis, Protonation and Cu II Complexes of Two Novel Isomeric Pentaazacyclophane Ligands: Potentiometric, DFT, Kinetic and AMP Recognition Studies

2008

The synthesis and coordination chemistry of two novel ligands, 2,6,9,12,16-pentaaza[17]metacyclophane (L1) and 2,6,9,12,16-pentaaza[17]paracyclophane (L2), is described. Potentiometric studies indicate that L1 and L2 form a variety of mononuclear complexes the stability constants of which reveal a change in the denticity of the ligand when moving from L1 to L2, a behaviour that can be qualitatively explained by the inability of the paracyclophanes to simultaneously use both benzylic nitrogen atoms for coordination to a single metal centre. In contrast, the formation of dinuclear hydroxylated complexes is more favoured for the paraL2 ligand. DFT calculations have been carried out to compare …

chemistry.chemical_classificationCoordination sphereDenticityLigandChemistryStereochemistryPotentiometric titrationProtonationCoordination complexInorganic Chemistrychemistry.chemical_compoundCrystallographyMoleculeCyclophaneEuropean Journal of Inorganic Chemistry
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ChemInform Abstract: Cryptand-Like Anion Receptors

2010

The design of supramolecular hosts for anions began with simple diaza bicycles, named katapinands, and has evolved over the last 40 years to a number of elegantly designed receptors capable of binding many different anions. About the same time the term cryptand appeared in reference to another bicyclic compound that was selective for alkaline-earth ions. Since the first report these simple bicycles, a vast arena of hosts has appeared, including acyclic, monocyclic, and other multicyclic supramolecular receptors. Studies of these systems have revealed considerable information about anion coordination chemistry, including the fact that many of these complexes mimic their transition-metal coro…

chemistry.chemical_classificationBicyclic moleculeChemistryCovalent bondCoordination numberCryptandSupramolecular chemistryGeneral MedicineCombinatorial chemistryIonCoordination complexChemInform
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Tritopic phenanthroline and pyridine tail-tied aza-scorpiands

2010

The synthesis of two new tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties have been linked with 2,6-dimethylpyridine (L1) or 2,9-dimethylphenanthroline (L2) units is reported for the first time. Their acid-base behaviour and Zn(2+) coordination chemistry have been studied by pH-metric titrations, molecular dynamic calculations, NMR, UV-Vis and steady-state fluorescence techniques. L1 and L2 behave, respectively, as hexaprotic and heptaprotic bases in the experimental conditions used (298.1 +/- 0.1 K, 0.15 mol dm(-3) NaCl, pH range under study 2.0-11.0). These ligands are able to form mono-, bi- and trinuclear Zn(2+) co…

chemistry.chemical_classificationStereochemistryPhenanthrolineOrganic ChemistryPotentiometric titrationBiochemistryFluorescenceMedicinal chemistryPyrophosphateCoordination complexchemistry.chemical_compoundMolecular dynamicschemistryPyridineTitrationPhysical and Theoretical ChemistryOrganic & Biomolecular Chemistry
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From isolated 1H-pyrazole cryptand anion receptors to hybrid inorganic-organic 1D helical polymeric anion receptors

2015

We report a novel 1-D helical coordination polymer formed by protonated polyamine 1H-pyrazole cryptands interconnected by Cu2+ metal ions that are able to encapsulate anionic species behaving as a multianion receptor. Switching from a monomeric receptor to a polymeric receptor is activated by metal ions and pH.

kemiaChemistryStereochemistryCoordination polymerMetal ions in aqueous solutionCryptandreceptorsProtonationPyrazolechemistryInorganic Chemistrychemistry.chemical_compoundMonomerPolymer chemistryPolyamineReceptorta116Dalton Transactions 44: 7761-7764 (2015)
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Structural reorganisation in polytopic receptors revealed by kinetic studies.

2010

One of the first kinetic studies of metal ion reorganisation between the different sites of a tritopic polyaza ligand reveals well defined pathways for the movement of the metal ion.

Spectrometry Mass Electrospray IonizationBinding SitesMacrocyclic CompoundsMagnetic Resonance SpectroscopyMolecular StructureStereochemistryChemistryLigandMetals and AlloysGeneral ChemistryKinetic energyLigandsCatalysisSurfaces Coatings and FilmsElectronic Optical and Magnetic MaterialsMetalCrystallographyKineticsvisual_artMaterials ChemistryCeramics and Compositesvisual_art.visual_art_mediumReceptorCopperChemical communications (Cambridge, England)
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Enhancement of SOD activity in boehmite supported nanoreceptors

2018

The binuclear Cu2+ complex of a pyridinophane polyamine ligand ranking amongst the fastest SOD mimetics so far reported displays a remarkable SOD activity enhancement when grafted to the surface of boehmite (γ-AlO(OH)) nanoparticles (BNPs).

Boehmite010405 organic chemistryLigandChemistryMetals and AlloysNanoparticleGeneral ChemistryQuímica010402 general chemistry01 natural sciencesCatalysis0104 chemical sciencesSurfaces Coatings and FilmsElectronic Optical and Magnetic Materialschemistry.chemical_compoundPolymer chemistryMaterials ChemistryCeramics and CompositesPolyamine
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Copper(ii) and Zn(ii) coordination chemistry of tetraaza[n]cyclophanes

2003

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…

chemistry.chemical_classificationStereochemistryPicrateProtonationGeneral ChemistryCrystal structureRing (chemistry)CatalysisSquare pyramidal molecular geometryCoordination complexchemistry.chemical_compoundCrystallographychemistryMaterials ChemistryMoleculeCoordination geometryNew J. Chem.
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Geometric Isomerism in Pentacoordinate Cu2+ Complexes: Equilibrium, Kinetic, and Density Functional Theory Studies Reveal the Existence of Equilibriu…

2009

A ligand (L1) (bis(aminoethyl)[2-(4-quinolylmethyl)aminoethyl]amine) containing a 4-quinolylmethyl group attached to one of the terminal amino groups of tris(2-aminoethyl)amine (tren) has been prepared, and its protonation constants and stability constants for the formation of Cu(2+) complexes have been determined. Kinetic studies on the formation of Cu(2+) complexes in slightly acidic solutions and on the acid-promoted complex decomposition strongly suggest that the Cu(2+)-L1 complex exists in solution as a mixture of two species, one of them showing a trigonal bipyramidal (tbp) coordination environment with an absorption maximum at 890 nm in the electronic spectrum, and the other one bein…

Models MolecularMagnetic Resonance SpectroscopyCations DivalentMolecular ConformationProtonationLigandsInorganic ChemistryIsomerismComputational chemistryMoleculePhysical and Theoretical ChemistryMolecular StructureChemistryLigandHydrolysisNuclear magnetic resonance spectroscopyHydrogen-Ion ConcentrationSquare pyramidal molecular geometryKineticsTrigonal bipyramidal molecular geometryCrystallographySpectrophotometryDensity functional theoryProtonsAcidsCopperCis–trans isomerismInorganic Chemistry
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CO2fixation and activation by metal complexes of small polyazacyclophanes

2001

The interaction of the cyclophanes 2,6,9,13-tetraaza[14]paracyclophane (L1) and 2,6,9,13-tetraaza[14]metacyclophane (L2) and of their Zn2+ and Cu2+ complexes with CO32− and its protonated forms is described. The actuation of the Cu2+–L2 system as an electrocatalyst for the reduction of CO2 to CO in water is advanced. Copyright © 2001 John Wiley & Sons, Ltd.

Metalchemistry.chemical_compoundchemistryvisual_artOrganic ChemistryCarbon fixationCarbon dioxideInorganic chemistryvisual_art.visual_art_mediumProtonationPhysical and Theoretical ChemistryElectrocatalystJournal of Physical Organic Chemistry
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A New ZnIITweezer Pyridine-Naphthalene System - An Off-On-Off System Working in a Biological pH Window

2005

Their basic idea consisted of the connec-tion of an amine to a fluorophoric anthracene unit on oneside and to a pyridine moiety on the other. At acidic pHvalues the amino and the pyridine groups are protonatedand a photoinduced electron transfer (PET) occurs fromthe π-π* excited state of the anthracene to the protonatedpyridinium unit, leading to quenching of the fluorescence.However, at high pH values, where the amino group is notprotonated, PET alternatively takes place from the aminelone pair to the same excited state of the fluorophore, yield-ing the same inhibitory effect on the fluorescence. Betweenthese two pH values, there is a pH window where PET doesnot take place and fluorescence…

Inorganic Chemistrychemistry.chemical_compoundAnthraceneFluorophoreQuenching (fluorescence)chemistryExcited statePyridineAmine gas treatingPhotochemistryFluorescencePhotoinduced electron transfer
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Stabilization of polyiodide networks with Cu(ii) complexes of small methylated polyazacyclophanes: shifting directional control from H-bonds to I⋯I i…

2020

Ordered polyiodide networks have recently gathered considerable attention as electronic materials, a topic historically dominated by metals. Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials? Herein we present a first principles study featuring three analogous polyazacyclophanes (L, L-Me, L-Me3), differing only in the extent of N-methylation. We demonstrate (potentiometry, ITC) how they all form the same CuL2+ (L = L, L-Me, L-Me3) complex as prevalent species in solution, so that a level playing field exists where only N-methylation distinguishes them. Then we use them as count…

Inorganic ChemistryMetalPolyiodidechemistry.chemical_compoundMaterials sciencechemistryRobustness (computer science)Chemical physicsvisual_artPairingvisual_art.visual_art_mediumElectronic materialsElectronic propertiesInorganic Chemistry Frontiers
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Cu2+and AMP complexation of enlarged tripodal polyamines

2006

The synthesis, characterization, Cu2+ coordination and interaction with AMP of three tripodal polyamines are reported. The polyamines are based on the structure of the tetraamine (tren) which has been enlarged with three propylamino functionalities (TAL), with a further anthrylmethyl fragment at one of its terminal primary nitrogens (ATAL) or with naphthylmethyl fragments at its three ends (N3TAL). The protonation constants of all three polyamines show that at pH 6, all six primary and secondary nitrogen atoms in the arms are protonated. The interaction with Cu2+ and AMP (adenosine-5′-monophosphate) has been studied by potentiometric, UV-Vis, ESI-MS spectroscopy and NMR techniques. pH-Metri…

Binding SitesAqueous solutionMolecular StructureStereochemistryChemistrySpectrum AnalysisPotentiometric titrationProtonationAdenosine MonophosphateAdductInorganic ChemistryParamagnetismPolyaminesPotentiometrySpectroscopyTernary operationCopperStoichiometryDalton Trans.
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CCDC 973978: Experimental Crystal Structure Determination

2013

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parametersbis(mu2-3711151819-hexaazabicyclo[15.2.1]icosa-1(19)17(20)-dien-18-yl)-carbonato-aqua-tri-copper(ii) diperchlorate octahydrateExperimental 3D Coordinates
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CCDC 973974: Experimental Crystal Structure Determination

2013

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bis(mu2-311151819-pentaaza-7-azoniabicyclo[15.2.1]icosa-1(19)17(20)-dien-18-yl)-di-copper(ii) triperchlorate hydrateSpace GroupCrystallographyCrystal SystemCrystal StructureCell ParametersExperimental 3D Coordinates
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CCDC 973976: Experimental Crystal Structure Determination

2013

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Space GroupCrystallographyCrystal System(37111521-pentaazabicyclo[15.3.1]henicosa-1(21)1719-triene)-copper(ii) diperchlorateCrystal StructureCell ParametersExperimental 3D Coordinates
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CCDC 1827335: Experimental Crystal Structure Determination

2018

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chloro-[6-methyl-39-bis(propan-2-yl)-36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-triene]-copper(ii) perchlorateSpace GroupCrystallographyCrystal SystemCrystal StructureCell ParametersExperimental 3D Coordinates
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CCDC 983275: Experimental Crystal Structure Determination

2015

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parameterscatena-[bis(mu3-1781420213233-octaaza-41117242936-hexaazoniapentacyclo[12.12.12.169.11922.13134]hentetraconta-6(41)819(40)2131(39)33-hexaene)-nonachloro-tri-copper nonakis(chloride) unknown solvate hydrate]Experimental 3D Coordinates
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CCDC 1030676: Experimental Crystal Structure Determination

2015

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parameters1781420213233-octaaza-41117242936-hexaazoniapentacyclo[12.12.12.169.11922.13134]hentetraconta-6(41)819(40)2131(39)33-hexaene hexakis(chloride) octahydrateExperimental 3D Coordinates
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CCDC 2017310: Experimental Crystal Structure Determination

2020

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parametersiodo-[6-methyl-36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-triene]-copper heptaiodideExperimental 3D Coordinates
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CCDC 1827337: Experimental Crystal Structure Determination

2018

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parametersaqua-[6-methyl-39-bis(propan-2-yl)-36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-triene]-copper(ii) bis(perchlorate) monohydrateExperimental 3D Coordinates
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CCDC 2017311: Experimental Crystal Structure Determination

2020

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parameters(369-trimethyl-36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-triene)-(tri-iodide)-copper penta-iodideExperimental 3D Coordinates
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CCDC 2017309: Experimental Crystal Structure Determination

2020

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Space GroupCrystallographyCrystal SystemCrystal Structure(36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-triene)-iodo-copper(ii) tri-iodideCell ParametersExperimental 3D Coordinates
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CCDC 973975: Experimental Crystal Structure Determination

2013

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Space GroupCrystallographyCrystal SystemCrystal Structurebis(mu2-3711151819-hexaazabicyclo[15.2.1]icosa-1(19)17(20)-dien-18-yl)-di-copper(ii) bromide perchlorate hydrateCell ParametersExperimental 3D Coordinates
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CCDC 1827336: Experimental Crystal Structure Determination

2018

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6-methyl-39-bis(propan-2-yl)-36915-tetraazabicyclo[9.3.1]pentadeca-1(15)1113-trien-6-ium perchlorate hemihydrateSpace GroupCrystallographyCrystal SystemCrystal StructureCell ParametersExperimental 3D Coordinates
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CCDC 973977: Experimental Crystal Structure Determination

2013

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Space GroupCrystallographyCrystal SystemCrystal StructureCell Parametersbis(mu~2~-3711151819-hexaazabicyclo[15.2.1]icosa-1(19)17(20)-dien-18-yl)-carbonato-aqua-di-copper diperchlorate octahydrateExperimental 3D Coordinates
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