0000000000033462
AUTHOR
Santiago V. Luis
showing 41 related works from this author
Outer and inner coordination sphere chemistry of polyazacyclophane platinum(II) complexes. Crystal structure of [PtBr4]2(H4L1) · H2O (L1 = 2,6,9,13-t…
1997
Abstract The interaction of PtCl42− with the new azaparacyclophane 2,5,8,11-tetraaza[12]paracyclophane (L2) has been studied by 1H, 13C and 195Pt NMR spectroscopy. Three different complexes are detected as a function of pH, all of them presenting cis-arrangement of nitrogen donors and chloride anions. In the first one, formed at acidic pH, the central nitrogen atoms of the macrocyclic are coordinating to Pt(II) while the benzylic nitrogens remain protonated. Deprotonation of these nitrogens brings about a reorganisation of the complex, and the platinum is then coordinated by one benzylic nitrogen and the consecutive nitrogen in the macrocycle. This process can be monitored by NMR. Finally, …
Studies on the interaction of phosphate anions with N-functionalised polyaza[n]paracyclophanes: the role of N-methylation.
2004
The synthesis and interaction of N,N',N'',N'''-tetramethyl-2,6,9,13-tetraaza[14]paracyclophanes (B323Me(4)) with nucleotides and inorganic phosphates is described. An easy methodology is used to define thermodynamic selectivity. The interaction of B323Me4 and ATP has been monitored by (1)H, (31)P NMR and by molecular mechanics, ruling out the possibility of the participation of pi-stacking interactions. Results show that N-methylation is accompanied by a strong increase in the interaction of the resulting macrocycle with ATP.
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 …
Thermodynamics of sulfate anion binding by macrocyclic polyammonium receptors
2001
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…
Chiral synthetic pseudopeptidic derivatives as triplet excited state quenchers
2009
The behavior of 6 pseudopeptidic models, synthesized by connecting different protected amino acids (Trp, Tyr, Phe, and Lys) with various diamino spacers, as quenchers of the triplet excited state of tiaprofenic acid (and its methyl ester), has been investigated. A series of quenching constants have been determined, which depend on the nature of the quencher and on the stereochemistry of the excited drug. A significant degree of stereodifferentiation has been found for the peptidomimetic synthesized with Phe and Tyr linked by a piperazine bridge. The obtained results support the utility of laser flash photolysis (LFP) as a tool to investigate the interactions between photoexcited drugs and s…
Open-chain polyamine ligands bearing an anthracene unit - Chemosensors for logic operations at the molecular level
2001
In this work the absorption and the fluorescence emission properties as well as the protonation sequence of three open chain polyamine ligands of different dimensions bearing an anthracene unit were studied. The protonation and stability constants with Ni2+, Cu2+, Zn2+, and Cd2+ have been determined in 0.15 mol·dm−3 NaCl at 298.1 ± 0.1 K. The values of both protonation and stability constants follow the expected trends according to the number of nitrogen donors, sequence of chelate rings and hydrophilic−hydrophobic balance. Chelation enhancement of the fluorescence emission (CHEF) was observed for some complexes of these ligands with Zn2+ and Cd2+. In contrast the analog complexes containin…
Photoluminescence Enhancement of CdSe Quantum Dots: A Case of Organogel–Nanoparticle Symbiosis
2012
Highly fluorescent organogels (QD-organogel), prepared by combining a pseudopeptidic macrocycle and different types of CdSe quantum dots (QDs), have been characterized using a battery of optical and microscopic techniques. The results indicate that the presence of the QDs not only does not disrupt the supramolecular organization of the internal fibrillar network of the organogel to a significant extent, but it also decreases the critical concentration of gelator needed to form stable and thermoreversible organogels. Regarding the photophysical properties of the QDs, different trends were observed depending on the presence of a ZnS inorganic shell around the CdSe core. Thus, while the core-s…
Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing
2016
Pseudopeptidic receptors containing ferrocene fragments have been prepared and their response to a series of anions was measured by a voltammetry of microparticles methodology. Such water-insoluble compounds yield anion-assisted reversible solid-state oxidations differing in their open-circuit potential and their midpeak potential recorded in cyclic voltammetric measurements. The difference between those potentials provides the individual thermodynamic contributions of electron and proton transfer, revealing that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry. The studied receptors are potentially interesting for potentiometric sensing, showing relat…
Interactions of diaryl-polyamines with nucleic acids. Allosteric effects with dinuclear copper complexes
2002
Abstract A series of α,ω-diarylamines with a variable number of ethylenediamine units between terminal naphthylrings shows dramatic affinity changes towards double-stranded nucleic acids, particularly upon complexation with Cu(II) ions. Metal salts alone have under the applied conditions only a negligible effect. The affinity of the metal-free ligands towards nucleic acids shows significant differences to those of the underlying polyamines, with a reversed stabilization of DNA instead of the usually observed preference for RNA. The affinity changes and preliminary NMR studies are in line with intercalation of naphthylrings into the double-stranded nucleic acid, which is hampered by complex …
Homogeneous and supported copper complexes of cyclic and open-chain polynitrogenated ligands as catalysts of cyclopropanation reactions
1999
CuI and CuII complexes of cyclic and open-chain polyaza compounds have been tested as catalysts in the benchmark cyclopropanation reaction of styrene with ethyl diazoacetate. In general, only small amounts of copper are needed to promote the reaction. The catalytic activity depends on the structure of the ligand, e.g. amine–amides are more efficient than polyamines, and on the oxidation state of copper, CuII being more active than CuI. Given that CuI is the active species, these changes of behavior must be related to the stabilities of the complexes. The nature of the counterion also has a noticeable influence on the catalytic activity, the role of which is discussed. XAS measurements sugge…
Thermodynamic and kinetic studies on the Cu2+ coordination chemistry of a novel binucleating pyridinophane ligandElectronic supplementary information…
2003
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…
One-pot synthesis of polyaza[n]naphthalenophanes and polyaza[n]anthracenophanes
1998
Abstract Pernosylated polyaza[n]cyclophanes 13–20 were prepared by a Richman-Atkins modified methodology. Deprotection under mild conditions gave polyaza[n]cyclophanes 21–28 . This methodology allows for the preparation of cyclophanes containing labile C-N bonds.
Unveiling anion-induced folding in tripodal imidazolium receptors by ion-mobility mass spectrometry.
2021
The anion-induced folding of tripodal imidazolium receptors has been investigated by NMR spectroscopy, electrospray ionization ion mobility mass spectrometry and DFT calculations. Such folding can be switched by anion release upon collision induced dissociation.
Tetraaza-2,2′-biphenylophanes: larger is not always more flexible. The role of intramolecular H-bonding in polyazamacrocycles
2002
Abstract Intramolecular H-bonding can explain the trends in conformational flexibility for tetraaza-2,2′-biphenylophanes obtained by NMR and molecular dynamics calculations.
Thermodynamics and fluorescence emission studies on potential molecular chemosensors for ATP recognition in aqueous solution †
1999
The interaction of the open-chain polyamine N-(3-aminopropyl)-N′-[3-(anthrylmethyl)aminopropyl]ethane-1,2-diamine (L) with the relevant anionic forms of adenosine 5′-triphosphate (ATP), adenosine 5′-diphosphate (ADP) and adenosine 5′-monophosphate (AMP) is described. Unambiguous criteria for defining thermodynamic selectivity based on the use of effective stability constants are presented. The interaction of L and several other topologically similar polyammonium receptors with ATP has been shown to occur through electrostatic and π-stacking intermolecular forces. The π-stacking binding mode is modulated by the protonation degree of ATP as indicated by fluorescence emission titrations. Evide…
Pertosylated polyaza[n](9,10)anthracenophanes
1997
Abstract Pertosylated polyaza[n](9,10)antracenophanes have been obtained in high yields by a modification of the Richman-Atkins methodology. Molecular Mechanics calculations as well as the crystal structure of the N,N′,N″,N‴-Tetratosyl-2,6,9,13-tetraaza[14](9,10)anthracenophane 4 derivative reveal the existence of a well defined cavity where both the aromatic moiety and the nitrogen donor atoms converge. Reduced mobility of the aliphatic chain is also observed as well as the presence of some strain at the benzylic positions.
Electrochemistry of copper complexes with polyaza[n]paracyclophanes. Influence of ATP as an exogen ligand on the relative stability of the Cu(II) and…
2000
Abstract Interaction of Cu 2+ with the macrocycle 2,6,9,13-tetraaza[14]paracyclophane (L) and ATP has been followed by pH-metric titration, cyclic voltammetry and differential pulse voltammetry (DPV). Mixed adduct species with various degrees of protonation were found to be stable for pH>4. In neutral and alkaline media reduction of mixed complexes occurs in a two-electron quasi-reversible step in contrast with binary Cu 2+ L complexes which display two successive one-electron couples. The potentiometric and voltammetric data suggest that in ternary adducts ATP binds to Cu 2+ ions through the phosphate chain and one N-site of the adenine ring system.
Structural Studies on Polyaza[n]paracyclophanes. A Molecular Mechanics and Crystallographic Study
1997
Abstract Structural analysis of polyaza[n]paracyclophanes 1-5 has been carried out by the use of molecular mechanics and other techniques. NMR data and molecular mechanics calculations show that conformations in which the polyamine chain is arching above the aromatic ring are prevalent in solution. The crystal structure of triprotonated durene derivative 2b agrees with those studies. Crystals of 3H+.2b are triclinic, space group P1, with a = 11.758(4) A, b = 13.870(5) A, c = 17.181(3) A, α = 96.66(2)°, β = 106.02(2)°, γ = 104.87(3)°, Z = 4, R1 = 0.072, wR2 = 0.18. Three different conformations are present in the crystal. Good agreement between the crystal structures and calculated conformat…
A polyazacyclophane containing two biphenyl subunits as a versatile cation and anion receptor
2002
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.
An efficient β-turn directed cyclization of simple peptidomimetics
1999
Abstract Chiral polyaza[n]para- and metacyclophanes are easily assembled starting from the appropriate bis(bromomethyl)arene and diamides obtained from aminoacids and alkylidenediamines. The corresponding ortho-derivatives could not be obtained. Molecular dynamics calculations suggest that those results can be explained through the participation of a β-turn like structure in the open chain intermediate, which is only important for para- and meta-derivatives.
New molecular catalysts for ATP cleavage. Criteria of size complementarity
2000
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.
Synthesis and protonation behaviour of the macrocycle 2,6,10,13,17,21-hexaaza[22]metacyclophane. Thermodynamic and NMR studies on the interaction of …
1996
Abstract The novel cyclophane receptor 2,6,10,13,17,21-hexaaza[22]metacyclophane (L) has been synthesised and characterised. The acid-base behaviour and interaction with ATP, ADP and AMP have been studied by potentiometry in 0.15 mol dm−3 at 298.1 K and multinuclear NMR. L presents in its protonated forms a molecular organization which enables its multipoint binding with nucleotides. Salt-bridge formation occur between the polyammonium sites of L and the phosphate chain of the nucleotides while π-stacking between the meta-phenylene subunit incorporated in the receptor and the adenine ring of the nucleotides.
Azonia spiro polyaza macrocycles containing biphenyl subunits as anion and cation receptors
2011
Abstract The reaction of N-Boc triprotected cyclam with bis(chloromethyl)biphenyl followed by the corresponding deprotection of the nitrogen atoms allows the preparation of receptor 3 containing an azonia spiro subunit. This receptor shows slightly increased basicity than cyclam, in particular for the formation of the appropriate triply charged species as a consequence of the reduced capacity of the structure present in 3 to stabilize the species with lower protonation degrees through the formation of intramolecular hydrogen bonds. The properties of 3 as a receptor for Cu2+ and Zn2+ and the anions derived from PO 4 3 − ( Pi ) , P 2 O 7 4 − ( PPi ) , P 3 O 10 5 − ( TPP ) and ATP have been st…
Steady-state fluorescence emission studies on polyazacyclophane macrocyclic receptors and on their adducts with hexacyanocobaltate(III)
1995
The steady-state fluorescence emission spectra of the azacyclophanes 2,5,8,11-tetraaza[12] paracyclophane (L1), 2,6,9,13-tetraaza[14]paracyclophane (L2), 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L3) and 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L4) as a function of pH have been measured. The fully protonated species of each cyclophane gives the highest fluorescence-emission quantum yield. The shapes of the titration curves have been explained by the existence of an electron-transfer quenching effect from a non-protonated amine to the benzene chromophore. This effect is greater for macrocycles in which the first deprotonated amine group is closer to the…
Synthetic methods for the preparation of polystyrene resins containing chiral polyamine chains
1998
Abstract The preparation of functionalized polystyrene-divinylbenzene resins containing functional groups derived from polyamine aliphatic chains has been studied. Best results are always obtained by direct alkylation of the polyamine with Merrifield's polymers, but double alkylation at both end of the polyamine is observed. The procedure is useful for the preparation of polymer containing different chiral and non-chiral polyamine functionalities.
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…
Polyaza[n](1,4)naphthalenophanes and polyaza[n](9,10)anthracenophanes
2002
Abstract A series of polyaza[n](1,4)naphthalenophanes and polyaza[n](9,10)anthracenophanes have been prepared by using the Fukuyama's protecting group (2- or 4-nitrophenyl sulfonyl) in a one-pot cyclization–deprotection reaction. Global yields for the purified products are comparable with those obtained for other polyazacyclophanes using the tosyl group as the amine protecting group. Their structural study has been carried-out by NMR showing a high rigidity for the smaller cycles and a more dynamic behaviour for the largest member of the series. The free energy barrier for the rotational equilibrium for compound 25 is about 3 kcal/mol lower than that calculated for analogous N-tosylated mac…
Polyaza[n]paracyclophanes as synthetic models of Zn containing enzymes. The role of a non coordinated nitrogen atom in the proximity of the metal
1997
Abstract 2,6,9,13-Tetraaza[14]paracyclophane ( 3, B323 ) represents a simple model for Zn containing enzymes like HCAII which possess additional reactive groups in the proximity of the metal center. The Zn 2+ . 3 complex shows notable catalytic activity for the hydrolysis of p -nitrophenyl acetate. Structural modifications of 3 which affect to the non coordinated nitrogen atom greatly modify the catalytic activity of the receptor.
Crystalline self-assembly induced by aromatic edge-to-face interactions: the crystal structure of 2,6,6,10-tetrabenzyl-2,10-diaza-6-azonia[11]paracyc…
2002
The crystal structure of 2,6,6,10-tetrabenzyl-2,10-diaza-6-azonia[11]paracyclophane bromide reveals several intermolecular aromatic edge-to-face interactions which are important in the three-dimensional growing of the crystalline structure. Molecular dynamics and semiempirical studies indicate that the conformer found in the crystal is not the most stable in solution confirming the important role that edge-to-face interactions play in the structural arrangement found in the solid state.
Bis(imidazolium) salts derived from amino acids as receptors and transport agents for chloride anions
2015
The binding properties of bis(imidazolium) hosts 1a–c derived from amino acids towards different anions have been studied by 1H NMR titration experiments in 95 : 05 CD3CN : H2O at 303 K, ESI-MS and theoretical calculations. Among this family, the salt 1c showed a strong and high selectivity for chloride anions. Transmembrane chloride transport activity has also been studied for the three bis(imidazolium) based transporters in POPC liposome models, and compound 1a was identified as an active chloride/nitrate exchanger.
Coordination of Cu2+ Ions to C2 Symmetric Pseudopeptides Derived from Valine
2010
The acid-base and coordination properties of a family of pseudopeptidic ligands with C(2) symmetry derived from valine (4a-e) have been studied using a variety of techniques as a model for metal coordination in peptides and proteins. The Cu(2+) cation has been selected for coordination studies, although, for comparison, some results for Zn(2+) are also presented. Good agreement has been obtained between the results obtained by potentiometric titrations, spectroscopic analysis, and mass spectrometry (ESI) studies. These results highlight the potential for the use of ESI MS for characterizing the nature of the complex species formed. Clearly, the Cu(2+) complexes are much more stable than the…
Hydrophobic effects in the stabilisation of copper(I) by the macrocyclic ligands 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane and 14,1…
1996
Abstract The interaction of Cu 2+ with the para -azacychlophanes 16,17,19,20-tetramethyl-2,6,9,13-tetraazal[14]paracyclophane (L1) and 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L2) has been studied by potentiometry, and direct microcalorimetry at 298.1±0.1 K in 0.15 mol dm −3 NaClO 4 . The stability constants (log K CuLi = 13.35(3), log K CuL2 = 9.32(4)) and the thermodynamic parameters ( ΔH ° CuL1 = −47.3(8) kJ mol −1 , ΔH ° CuL2 = 20.9(8) kJ mol −1 ) evidence that not all four nitrogen atoms in the ligands are involved in the coordination to the metal centre. These results, particulary in the case of L1, are similar to those reported for the analogous cyclophanes contai…
Structural characterization in solution of multifunctional nucleotide coordination systems
2000
The interaction in aqueous solution of the cyclophane receptors 2,6,10,13,17,21-hexaaza[22]orthocyclophane (L11) and 2,6,10,13,17,21-hexaaza[22]paracyclophane (L22) with the nucleotides ATP, ADP and AMP has been studied by pH titration and NMR. The obtained results are compared with those previously reported for the analogous meta-substituted receptor 2,6,10,13,17,21-hexaaza[22]metacyclophane (L). All the experimental data support the actuation of these cyclophane molecules as multi-point binders of nucleotides through electrostatic, hydrogen bonding and π-stacking interactions. The combined use of NMR and molecular dynamics permits us to get a rather reliable picture of the way in which th…
1,4,8,11-Tetrakis(4-ferrocenyl-3-azabutyl)-1,4,8,11-tetraazacyclotetradecane as a ferrocene-functionalised polyammonium receptor for electrochemical …
1999
The interaction of the ferrocene-functionalised polyaza receptor 1,4,8,11-tetrakis(4-ferrocenyl-3-azabutyl)-1,4,8,11-tetraazacyclotetradecane (L1) with sulfate, phosphate and ATP has been studied potentiometrically in THF–water 70∶30 v/v (0.1 mol dm–3 tetrabutylammonium perchlorate, 25 °C). The molecular structure of the free receptor has been determined by single-crystal X-ray procedures. An electrochemical study on L1 as a function of the pH has been carried out in THF–water 70∶30 v/v in the presence of the sulfate, phosphate and ATP anions. The potential use of L1 as an anion sensing receptor is discussed in terms of the electrochemical and potentiometric data and its behaviour is compar…
New strategies in the development of polynuclear complexes. Crystal structure of the tetranuclear copper(II) complex [Cu4(L1)2(OH)4Cl2(H2O)2]2(H3O2)(…
2000
Abstract The preparation and interaction of the new polyaza[n]naphthalenophanes 2,5,8,11-tetraaza[12](1,4)naphthalenophane (L1) and 2,6,9,13-tetraaza[14](1,4)naphthalenophane (L2) with hydrogen ions and Cu2+ is described. The crystal structure of the new tetranuclear copper(II) complex [Cu4(L1)2(OH)4Cl2(H2O)2]2(H3O2)(ClO4)2Cl·2H2O (L1=2,5,8,11-tetraaza[12](1,4)naphthalenophane) is presented and discussed. A variety of intra- and intermolecular forces contribute to the particular organisation of the crystal. The solution studies indicate the formation of similar tetranuclear species for L1 while for L2 just mononuclear 1:1 species are detected.
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.
Dual stereocontrolled alkylation of aldehydes with polystyrene-supported nickel complexes derived from α-amino amides
2015
Nickel(II) complexes derived from α-amino amide ligands anchored to gel-type and monolithic polymers act as efficient catalysts for the enantioselective addition of dialkylzinc reagents to aldehydes. Similar to the analogous homogeneous systems, dual stereocontrol in addition products can be achieved by controlling the stoichiometry of the immobilized nickel complex. Aromatic and aliphatic aldehydes were alkylated in good yields with enantioselectivities comparable to those obtained with the homogeneous analogues. These polymer-supported catalysts offer significant advantages as no metal leaching is observed and they can be easily recovered from the reaction mixture by simple filtration and…
Polyamines containing naphthyl groups as pH-regulated molecular machines driven by light
2001
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
Copper complexes of polyaza[n]cyclophanes and their interaction with DNA and RNA
2001
Abstract The complexation properties of Cu 2+ ions with the cyclophane receptors 2,6,9,13-tetraaza[14]metacyclophane ( L1 ), 2,6,10,13,17,21-hexaaza[22]metacyclophane ( L2 ) and 2,6,10,13,17,21-hexaaza[22]paracyclophane ( L3 ) are presented. Formation of mononuclear complexes in the case of L1 and of mono- and binuclear complexes in the case of the hexaaazcyclophane ligands L2 and L3 is observed. The coordination numbers around each Cu 2+ in the binuclear complexes involve at most three nitrogen donors for each metal ion. Cyclophanes L1 – L3 and several acyclic polyamine ligands are tested for their affinity towards double-stranded nucleic acid models of RNA and DNA. The binding affinity of…
A remarkable selectivity in the N-functionalization of polyaza[n]paracyclophanes. Synthesis of N-(4-picolyl)-substituted 2,6,9,13-tetraaza[14]paracyc…
1997
Abstract Interaction of cationic host species, in particular Zn 2+ salts, with polyaza[n]paracyclophanes (i.e. 2,6,9,13-Tetraaza[14]paracyclophane, B323 (1a) ) directs their selective N-functionalization. In this way compounds mono- or difunctionalized with ArCH 2− groups at the benzylic nitrogen atoms can be easily obtained. Direct reaction with the alkylating agent, in the absence of the Zn 2+ species, produces, in general, very complex mixtures of mono- and polyalkylated compounds except when 4-picolyl chloride is used. In this case, mono-, di-, tri- and tetra N-substituted derivatives of D323 can be isolated depending on the amount of the alkylating agent used. In this case, the mono- a…
Oxaaza cyclophanes in the recognition of nucleotides. The role of oxygen and electron-rich aromatic rings
2007
Dioxapolyaza cyclophanes derived from resorcinol and different polyamine chains have been studied in aqueous solution as abiotic receptors for nucleotides. The presence of the additional ethyleneoxy subunits is reflected in a higher basicity and in a significant increase in the log K values for the interaction with nucleotides relative to that of related polyazacyclophanes.